Biogenic non-crystalline U(IV) revealed as major component in uranium ore deposits

Science.gov (United States)

Bhattacharyya, Amrita; Campbell, Kate M.; Kelly, Shelly D.; Roebbert, Yvonne; Weyer, Stefan; Bernier-Latmani, Rizlan; Borch, Thomas

2017-06-01

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U(VI)) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U(IV) generated through biologically mediated U(VI) reduction is the predominant U(IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (~58-89%) of U is bound as U(IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U(VI) represent only minor components. The uranium deposit exhibited mostly 238U-enriched isotope signatures, consistent with largely biotic reduction of U(VI) to U(IV). This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U(IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.

Coordination phenomena of cationic uranium(iv) complexes

International Nuclear Information System (INIS)

Rohwer, H.E.

1974-12-01

The coordination properties of the cationic uranium(IV) complexes UCl 3 + , UCl 2 2+ , UCl 3+ , and U 4+ were studied in a non-aqueous medium in the presence of perchlorate as counterion which, however, proved to coordinate to a much greater extent than expected. The strong neutral ligand, HMPA, could successively displace some of the perchlorates. An electrostatic model for the U(CIO 4 ) 4 -HMPA-acetone system compared favourably with the actual results. This emphasized the high ionic content in the bonding with actenoid cations, even with such a high charge as +4 . These conclusions are in agreement with studies 75 in which nitrate acts as counter ion. Correspondingly the uranium (IV) chemistry is characterized by the absence of typical 3d-organometallic chemistry, for example, strong bonding with CO, P(Phi) 3 etc, which strongly depends on covalent bonding. This stresses the fact that the d and f orbitals are not readily available for strong bond formation with the actenoids. 76

Uranium removal during low discharge in the Ganges-Brahmaputra mixing zone

International Nuclear Information System (INIS)

Carroll, J.; Moore, W.S.

1993-01-01

The Ganges-Brahmaputra river system supplies more dissolved uranium to the ocean than any other system in the world (Sarin et al., 1990; Sackett et al., 1973). However, there have been no investigations to determine whether riverine supplies of uranium are altered by geochemical reactions in the river-ocean mixing zone. In this study, uranium and salinity data were collected in the Ganges-Brahmaputra mixing zone during a period of low river discharge. The uranium distribution with salinity shows that in waters <12 ppt salinity, uranium activities are significantly lower than predicted from conservative mixing of river and seawater. This suggests that uranium is being removed within the mixing zone. The behavior of uranium in the Ganges-Brahmaputra is in sharp contrast to its behavior in the Amazon mixing zone where McKee et al. (1978) found uranium activities significantly higher than predicted from conservative mixing. The contrasting behaviors for uranium in these systems are due to the different locations where mixing between river and seawater occurs. For the Amazon, mixing takes place on the continental shelf whereas for the Ganges-Brahmaputra, mixing occurs within shoreline sedimentary environments. The physiochemical processes controlling uranium removal to sediment deposits in the Amazon are partly known. The authors discuss mechanisms which may be removing uranium to suspended and mangrove sediments in the Ganges-Brahmaputra

Study of aqueous complexes of uranium (IV) in an acid medium by nuclear magnetic resonance

International Nuclear Information System (INIS)

Kiener, C.; Folcher, G.; Rigny, P.; Virlet, J.

1976-01-01

The hydration of tetravalent uranium in acid solutions has been studied by proton magnetic resonance. Longitudinal and transversal relaxation rates of water are reported as a function of temperature, acidity, and added ions. The relaxation rates observed in perchloric solutions at high temperature are governed by the exchange process of water molecules between the inner coordination sphere of uranium(IV) and the bulk water. The bound proton's lifetime lies between 10 ms and 1 s. At pH > 0, the exchange rate depends upon acidity according to a simple expression. At high concentrations of diamagnetic ions the exchange rate depends linearly upon water activity. At low temperature, the proton relaxation rates are dominated by an outer sphere effect and the electronic relaxation time of uranium(IV) is found to be about 10 -13 s. No signal is observed from protons of the water molecules in the first sphere, firmly bound to uranium(IV), which undergo rapid relaxation. The chemical shift of the proton absorption signal in hydrochloric solutions arise from tightly bound water molecules in paramagnetic interaction with uranium(IV) in a second sphere, and in fast exchange with the bulk water. Above a chlorine concentration of 6 M, the monochloro complex of uranium(IV) contributes to the chemical shift. (author)

Synthesis and characterization of thorium(IV) and uranium(IV) complexes with Schiff bases

Energy Technology Data Exchange (ETDEWEB)

Radoske, Thomas; Maerz, Juliane; Kaden, Peter; Patzschke, Michael; Ikeda-Ohno, Atsushi [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Chemistry of the F-Elements

2017-06-01

We report herein the synthesis and characterization of several imine complexes of tetravalent thorium (Th(IV)) and uranium (U(IV)). The ligands investigated in this study are a Schiff base type, including the well-known salen ligand (H{sub 2}Le, Fig. 1). The complexation in solution was investigated by NMR measurements indicating paramagnetic effects of unpaired f-electrons of U(IV) on the ligand molecule. We also determined the solid-state molecular structures of the synthesized complexes by single crystal X-ray diffraction. The synthesized complexes show an eight-fold coordination geometry around the actinide center surrounded by two tetradentate ligands with 2N- and 2O-donor atoms.

The kinetics of the cerium(IV)-uranium(IV) reaction at low sulfate concentrations

International Nuclear Information System (INIS)

Michaille, P.; Kikindai, T.

1977-01-01

The rate of oxidation of uranium(IV) by cerium(IV) was measured with a stopped-flow spectrophotometer at sulfuric acid concentrations of 2 x 10 -6 to 0.5 M. At a constant hydrogen ion concentration of 0.5 M, the maximum rate constant was observed for 2 x 10 -3 M sulfuric acid; at that concentration, two sulfate ions were involved in the activated complex. The dependence of the rate constant on the hydrogen ion concentration showed that the reaction paths involving one or two sulfate ions also involved one hydroxyl ion, whereas one hydrogen ion was involved in the five sulfate dependent path. Spectrophotometric measurements supported the existence of a hydrolyzed monosulfatocomplex of cerium(IV). (author)

Solubility Determination of Uranium (IV) Oxalates U(C2O4)2.6H2O and M2U2(C2O4)5.nH2O (M = mono-charged cation)

International Nuclear Information System (INIS)

Costenoble, Sylvain; Grandjean, Stephane; Arab-Chapelet, Benedicte; Abraham, Francis

2008-01-01

The solubility of uranium (IV) oxalate compounds was studied in order to have a precise insight of the behaviour of An(IV)-An(III) (An(IV) = U, Np or Pu and An(III) = Pu or Am) mixed oxalate in the context of oxalic co-conversion for actinide co-management. Concepts of thermodynamics of aqueous-solid solution are reviewed by introducing LIPPMANN theory and THORSTENSON and PLUMMER 'stoichiometric saturation' model in a way to understand and model the system of interest. Different analytical techniques have been developed in order to titrate uranium and/or other actinides at trace levels in solution. This thorough investigation is the basis of further experiments on the solubility of mixed U(IV)- An(III) oxalate solid solutions as a function of the nature of the trivalent actinide and the An(III)/U(IV) ratio. (authors)

Sorption of uranium on rocks in anaerobic groundwater

International Nuclear Information System (INIS)

Hakanen, M.

1992-12-01

Spent nuclear fuel contains substantial amounts of long lived isotopes of actinoide elements, the most abundant of which is the oxide from uranium in the fuel matrix. The behaviour of uranium, also present in small concentrations in natural rocks and waters, is redox sensitive. The concentration controlling mechanisms in groundwaters of uranium are not well-known. In this work a series of laboratory experiments was made to study the redox and sorption behaviour of uranium under anaerobic conditions. The experiments indicated that a part of uranium(VI) was reduced to uranium(IV). The sorbed uranium was of mixed oxidation states. The redox potential of water was not an appropriate indicator of the U(IV)/U(VI) ratio. Spiking of the water with the U(IV) was followed by very strong sorption. The derived lower limit (conservative) and the realistic mass distribution ratios (R d ) for U(IV) are 0.7 m 3 /kg and 3.5 m 3 /kg. (orig.)

Electrochemical behaviour of uranium (IV) in DMF at vitreous carbon

International Nuclear Information System (INIS)

Afonso, M.L.; Gomes, A.; Carvalho, A.; Alves, L.C.; Wastin, F.; Goncalves, A.P.

2009-01-01

The electrochemical behaviour of UCl 4 (0.01 mol L -1 up to 0.05 mol L -1 ) in 0.1 mol L -1 TBAPF 6 /DMF solution at vitreous carbon was studied, at room temperature, by cyclic voltammetry and potentiostatic techniques. The electrolytic solutions were analyzed by UV spectroscopy (UV), and the electrodeposited films were characterized by Rutherford Backscattering Spectroscopy (RBS) and X-ray diffraction (XRD). The cyclic voltammetric results, at low UCl 4 concentrations (0.01 mol L -1 ), point that the reduction of U(IV) to U(0) occurs in two steps involving mainly U(IV) and U(III) species. The first electron transfer reaction is quasi-reversible and the second irreversible. The diffusion coefficient of U(IV) in DMF and the charge rate constant were determined to be 4.78 x 10 -7 cm 2 s -1 and 1.93 x 10 -3 cm s -1 (at 0.02 V s -1 ), respectively. RBS data obtained from samples prepared at constant potential (-3.10 V) during 3 h at room temperature, indicated the presence of uranium particles deposited all over the vitreous carbon surface with aggregates in some places, confirming that the second reduction step corresponds to uranium electrodeposition. No crystallographic ordering could be seen by XRD, pointing to an amorphous character of the uranium films.

Nuclear fuel technology - Determination of uranium in solutions, uranium hexafluoride and solids - Part 2: Iron(II) reduction/cerium(IV) oxidation titrimetric method

International Nuclear Information System (INIS)

2004-01-01

This first edition of ISO 7097-1 together with ISO 7097-2:2004 cancels and replaces ISO 7097:1983, which has been technically revised, and ISO 9989:1996. ISO 7097 consists of the following parts, under the general title Nuclear fuel technology - Determination of uranium in solutions, uranium hexafluoride and solids: Part 1: Iron(II) reduction/potassium dichromate oxidation titrimetric method; Part 2: Iron(II) reduction/cerium(IV) oxidation titrimetric method. This part 2. of ISO 7097 describes procedures for determination of uranium in solutions, uranium hexafluoride and solids. The procedures described in the two independent parts of this International Standard are similar: this part uses a titration with cerium(IV) and ISO 7097-1 uses a titration with potassium dichromate

Extraction and Separation of Uranium (VI) and Thorium (IV) Using Tri-n-dodecylamine Impregnated Resins

International Nuclear Information System (INIS)

Metwally, E.; Saleh, A.Sh.; El-Naggar, H.A.

2005-01-01

Extraction of U(VI) and Th(IV) from chloride and nitrate solutions with tri-n- dodecylamine impregnated on Amberlite XAD4, was investigated. The distribution of U(VI) and Th(IV) was studied at different concentrations of acid, salting-out agent, extractant, aqueous metal ion and other parameters. Absorption spectral studies have been investigated for uranium species in both aqueous HCl solution and the resin phase. From these studies, it is suggested that the tetrachloro complex of U(VI) is formed in the extraction of uranium (VI) from hydrochloric acid solutions by TDA impregnated resin. Stripping of the extracted U(VI) and Th(IV) was assayed with HCl and HNO 3 . Finally, the separation of uranium from thorium and fission products in HCl media was achieved

Preparation of uranium-based oxide catalysts; Preparation de catalyseurs oxydes a base d'uranium

Energy Technology Data Exchange (ETDEWEB)

Bressat, R [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1965-07-01

We have studied the thermal decomposition of uranyl and uranium IV oxalates as a mean of producing uranium dioxide. We have isolated the main intermediate phases of the decompositions and have indexed the lines of their X-ray diffraction patterns. The oxides produced by the decomposition are ill-defined and unstable: they strongly absorb atmospheric oxygen with modification of the composition and, in certain cases, of the structure (pyrophoric oxide). With a view to obtaining stable oxides, we have prepared mixed uranium-thorium oxalates. In order to prepare an oxalate having a homogeneous composition, it is necessary to adopt a well-defined preparation method: the addition of solutions of thorium and uranium IV nitrates to a continually saturated oxalic acid solution. The mixed oxide obtained from the thermal decomposition of an oxalate U{sub x}Th{sub 1-x}(C{sub 2}O{sub 4}){sub 2}, 2 H{sub 2}O at 500 C for 24 hours in a current of oxygen leads to a cubic structure which is well-defined both in the bulk and superficially when x is less than 0.35. Above this atomic concentration of uranium, some uranium moves out of the lattice in the form of UO{sub 3} or U{sub 3}O{sub 8} according to the temperature. The mixed oxide is not stoichiometric,(U{sub x}Th{sub 1-x}O{sub 2+y}) and the average degree of oxidation of the uranium varies with the temperature and partial oxygen pressure. The oxides thus formed have a high surface area. By dissolving the mixed oxalates in a concentrated solution of ammonium oxalate, it is possible to deposit the catalyst on a support, but the differences in the solubilities of the thorium and uranium IV oxalates in the ammonium oxalate make it impossible to prepare double salts formed either of thorium and uranium and of ammonium. (author) [French] Nous avons etudie la decomposition thermique des oxalates d'uranyle et d'uranium IV en vue d'aboutir au dioxide d'uranium. Nous avons pu isoler les principales phases intermediaires des decompositions

Mixed Uranium/Refractory Metal Carbide Fuels for High Performance Nuclear Reactors

International Nuclear Information System (INIS)

Knight, Travis; Anghaie, Samim

2002-01-01

Single phase, solid-solution mixed uranium/refractory metal carbides have been proposed as an advanced nuclear fuel for advanced, high-performance reactors. Earlier studies of mixed carbides focused on uranium and either thorium or plutonium as a fuel for fast breeder reactors enabling shorter doubling owing to the greater fissile atom density. However, the mixed uranium/refractory carbides such as (U, Zr, Nb)C have a lower uranium densities but hold significant promise because of their ultra-high melting points (typically greater than 3700 K), improved material compatibility, and high thermal conductivity approaching that of the metal. Various compositions of (U, Zr, Nb)C were processed with 5% and 10% metal mole fraction of uranium. Stoichiometric samples were processed from the constituent carbide powders, while hypo-stoichiometric samples with carbon-to-metal (C/M) ratios of 0.92 were processed from uranium hydride, graphite, and constituent refractory carbide powders. Processing techniques of cold uniaxial pressing, dynamic magnetic compaction, sintering, and hot pressing were investigated to optimize the processing parameters necessary to produce high density (low porosity), single phase, solid-solution mixed carbide nuclear fuels for testing. This investigation was undertaken to evaluate and characterize the performance of these mixed uranium/refractory metal carbides for high performance, ultra-safe nuclear reactor applications. (authors)

Reactivity of uranium(IV) bridged chalcogenido complexes UIV–E–UIV (E = S, Se) with elemental sulfur and selenium: synthesis of polychalcogenido-bridged uranium complexes

OpenAIRE

Franke, Sebastian M.; Heinemann, Frank W.; Meyer, Karsten

2014-01-01

We report the syntheses, electronic properties, and molecular structures of a series of polychalcogenido-bridged dinuclear uranium species. These complexes are supported by the sterically encumbering but highly flexible, single N-anchored tris(aryloxide) chelator (AdArO)3N3−. Reaction of an appropriate uranium precursor, either the U(III) starting material, [((AdArO)3N)U(DME)], or the dinuclear mono-chalcogenido-bridged uranium(IV/IV) compounds [{((AdArO)3N)U(DME)}2(μ-E)] (E = S, Se), with el...

Uranium leaching using mixed organic acids produced by Aspergillus niger

International Nuclear Information System (INIS)

Yong-dong Wang; Guang-yue Li; De-xin Ding; Zhi-xiang Zhou; Qin-wen Deng; Nan Hu; Yan Tan

2013-01-01

Both of culture temperature and pH value had impacts on the degree of uranium extraction through changing types and concentrations of mixed organic acids produced by Aspergillus niger, and significant interactions existed between them though pH value played a leading role. And with the change of pH value of mixed organic acids, the types and contents of mixed organic acids changed and impacted on the degree of uranium extraction, especially oxalic acid, citric acid and malic acid. The mean degree of uranium extraction rose to peak when the culture temperature was 25 deg C (76.14 %) and pH value of mixed organic acids was 2.3 (82.40 %) respectively. And the highest one was 83.09 %. The optimal culture temperature (25 deg C) of A. niger for uranium leaching was different from the most appropriate growing temperature (37 deg C). (author)

Fabrication of chamfered uranium-plutonium mixed carbide pellets

International Nuclear Information System (INIS)

Arai, Yasuo; Iwai, Takashi; Shiozawa, Kenichi; Handa, Muneo

1985-10-01

Chamfered uranium-plutonium mixed carbide pellets for high burnup irradiation test in JMTR were fabricated in glove boxes with purified argon gas. The size of die and punch in a press was decided from pellet densities and dimensions including the angle of chamfered parts. No chip or crack caused by adopting chamfered pellets was found in both pressing and sintering stages. In addition to mixed carbide pellets, uranium carbide pellets used as insulators were also successfully fabricated. (author)

Studies on O/M ratio determination in uranium oxide, plutonium oxide and uranium-plutonium mixed oxide

International Nuclear Information System (INIS)

Sampath, S.; Chawla, K.L.

1975-01-01

Thermogravimetric studies were carried out in unsintered and sintered samples of uranium oxide, plutonium oxide and uranium-plutonium mixed oxide under different atmospheric conditions (air, argon and moist argon/hydrogen). Moisture loss was found to occur below 200 0 C for uranium dioxide samples, upto 700 0 C for sintered plutonium dioxide and negligible for sintered samples. The O/M ratios for non-stoichiometric uranium dioxide (sintered and unsintered), plutonium dioxide and mixed uranium and plutonium oxides (sintered) could be obtained with a precision of +- 0.002. Two reference states UOsub(2.000) and UOsub(2.656) were obtained for uranium dioxide and the reference state MOsub(2.000) was used for other cases. For unsintered plutonium dioxide samples, accurate O/M ratios could not be obtained of overlap of moisture loss with oxygen loss/gain. (author)

A mononuclear uranium(IV) single-molecule magnet with an azobenzene radical ligand

Energy Technology Data Exchange (ETDEWEB)

Antunes, Maria A.; Coutinho, Joana T.; Santos, Isabel C.; Marcalo, Joaquim; Almeida, Manuel; Pereira, Laura C.J. [C" 2TN, Instituto Superior Tecnico, Universidade de Lisboa, Bobadela (Portugal); Baldovi, Jose J.; Gaita-Arino, Alejandro; Coronado, Eugenio [Instituto de Ciencia Molecular, Universitat de Valencia, Paterna (Spain)

2015-12-01

A tetravalent uranium compound with a radical azobenzene ligand, namely, [{(SiMe_2NPh)_3-tacn}U{sup IV}(η{sup 2}-N{sub 2}Ph{sub 2{sup .}})] (2), was obtained by one-electron reduction of azobenzene by the trivalent uranium compound [U{sup III}{(SiMe_2NPh)_3-tacn}] (1). Compound 2 was characterized by single-crystal X-ray diffraction and {sup 1}H NMR, IR, and UV/Vis/NIR spectroscopy. The magnetic properties of 2 and precursor 1 were studied by static magnetization and ac susceptibility measurements, which for the former revealed single-molecule magnet behaviour for the first time in a mononuclear U{sup IV} compound, whereas trivalent uranium compound 1 does not exhibit slow relaxation of the magnetization at low temperatures. A first approximation to the magnetic behaviour of these compounds was attempted by combining an effective electrostatic model with a phenomenological approach using the full single-ion Hamiltonian. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Magnetic-superexchange interactions of uranium(IV) chloride-addition complexes with amides, 2

International Nuclear Information System (INIS)

Miyake, Chie; Hinatsu, Yukio; Imoto, Shosuke

1983-01-01

The magnetic susceptibilities of five cyclic amide (lactam)-addition complexes of uranium(IV) chloride were measured between room temperature and 2 K. Magnetic-exchange interaction was found only for N-methyl-substituted amide complexes, and a dimer structure was assumed for them on the basis of their chemical properties. Treating interdimer interaction with a molecular-field approximation, the magnetic susceptibilities were calculated to be in good agreement with the experimental results in the temperature region of the maxima in chi sub(A). The transmission of antiparallel spin coupling via the π orbitals of the bridging amide ligands is proposed to explain the strong intradimer superexchange interaction for the uranium(IV) chloride-amide complexes with the magnetic-susceptibility maximum. (author)

Research on calculation of mixing fraction for natural uranium equivalent fuel

International Nuclear Information System (INIS)

Huang Shien; Wang Lianjie; Wei Yanqin; Li Qing; Zheng Jiye

2013-01-01

Based on the first-order perturbation theory and reasonable approximations, the calculation method of recycled uranium (RU) and depleted uranium (DU) mixing fraction for natural uranium equivalent (NUE) fuel was studied, so the equivalence between NUE fuel and natural uranium (NU) fuel was assured. The adopted calculation method accurately takes the variation of micro cross sections alone with fuel depletion into account. A computer code named ALPHA was programmed to execute the calculation procedure. Then the ALPHA code and the WIMS-AECL code compose a processing system, which is applicable to the mixing fraction calculation for heavy water reactor NUE fuel. The validation shows that the processing system can accurately calculate the mixing fraction for NUE fuel. (authors)

Synthesis, sintering and dissolution of thorium and uranium (IV) mixed oxide solid solutions: influence of the method of precursor preparation; Synthese, frittage et caracterisation de solutions solides d'oxydes mixtes de thorium et d'uranium (IV): influence de la methode de preparation du precurseur

Energy Technology Data Exchange (ETDEWEB)

Hingant, N

2008-12-15

Mixed actinide dioxides are currently considered as potential fuels for the third and fourth generations of nuclear reactors. In this context, thorium-uranium (IV) dioxide solid solutions were studied as model compounds to underline the influence of the method of preparation on their physico-chemical properties. Two methods of synthesis, both based on the initial precipitation of oxalate precursors have been developed. The first consisted in the direct precipitation ('open' system) while the second involved hydrothermal conditions ('closed' system). The second method led to a significant improvement in the crystallization of the samples especially in the field of the increase of the grain size. In these conditions, the formation of a complete solid solution Th{sub 1-x}U{sub x}(C{sub 2}O{sub 4}){sub 2}.2H{sub 2}O was prepared between both end-members. Its crystal structure was also resolved. Whatever the initial method considered, these compounds led to the final dioxides after heating above 400 C. The various steps associated to this transformation, involving the dehydration of precursors then the decomposition of oxalate groups have been clarified. Moreover, the use of wet chemistry methods allowed to reduce the sintering temperature of the final thorium-uranium (IV) dioxide solid solutions. Whatever the method of preparation considered, dense samples (95% to 97% of the calculated value) were obtained after only 3 hours of heating at 1500 C. Additionally, the use of hydrothermal conditions significantly increased the grain size, leading to the reduction of the occurrence of the grain boundaries and of the global residual porosity. The significant improvement in the homogeneity of cations distribution in the samples was also highlighted. Finally, the chemical durability of thorium-uranium (IV) dioxide solid solutions was evaluated through the development of leaching tests in nitric acid. The optimized homogeneity especially in terms of the

The utilization of uranium industry technology and relevant chemistry to leach uranium from mixed-waste solids

International Nuclear Information System (INIS)

Mattus, A.J.; Farr, L.L.

1991-01-01

Methods for the chemical extraction of uranium from a number of refractory uranium-containing minerals found in nature have been in place and employed by the uranium mining and milling industry for nearly half a century. These same methods, in conjunction with the principles of relevant uranium chemistry, have been employed at the Oak Ridge National Laboratory (ORNL) to chemically leach depleted uranium from mixed-waste sludge and soil. The removal of uranium from what is now classified as mixed waste may result in the reclassification of the waste as hazardous, which may then be delisted. The delisted waste might eventually be disposed of in commercial landfill sites. This paper generally discusses the application of chemical extractive methods to remove depleted uranium from a biodenitrification sludge and a storm sewer soil sediment from the Y-12 weapons plant in Oak Ridge. Some select data obtained from scoping leach tests on these materials are presented along with associated limitations and observations which might be useful to others performing such test work. 6 refs., 2 tabs

The utilization of uranium industry technology and relevant chemistry to leach uranium from mixed-waste solids

Energy Technology Data Exchange (ETDEWEB)

Mattus, A.J.; Farr, L.L.

1991-01-01

Methods for the chemical extraction of uranium from a number of refractory uranium-containing minerals found in nature have been in place and employed by the uranium mining and milling industry for nearly half a century. These same methods, in conjunction with the principles of relevant uranium chemistry, have been employed at the Oak Ridge National Laboratory (ORNL) to chemically leach depleted uranium from mixed-waste sludge and soil. The removal of uranium from what is now classified as mixed waste may result in the reclassification of the waste as hazardous, which may then be delisted. The delisted waste might eventually be disposed of in commercial landfill sites. This paper generally discusses the application of chemical extractive methods to remove depleted uranium from a biodenitrification sludge and a storm sewer soil sediment from the Y-12 weapons plant in Oak Ridge. Some select data obtained from scoping leach tests on these materials are presented along with associated limitations and observations which might be useful to others performing such test work. 6 refs., 2 tabs.

Preparation of uranium-based oxide catalysts; Preparation de catalyseurs oxydes a base d'uranium

Energy Technology Data Exchange (ETDEWEB)

Bressat, R. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1965-07-01

We have studied the thermal decomposition of uranyl and uranium IV oxalates as a mean of producing uranium dioxide. We have isolated the main intermediate phases of the decompositions and have indexed the lines of their X-ray diffraction patterns. The oxides produced by the decomposition are ill-defined and unstable: they strongly absorb atmospheric oxygen with modification of the composition and, in certain cases, of the structure (pyrophoric oxide). With a view to obtaining stable oxides, we have prepared mixed uranium-thorium oxalates. In order to prepare an oxalate having a homogeneous composition, it is necessary to adopt a well-defined preparation method: the addition of solutions of thorium and uranium IV nitrates to a continually saturated oxalic acid solution. The mixed oxide obtained from the thermal decomposition of an oxalate U{sub x}Th{sub 1-x}(C{sub 2}O{sub 4}){sub 2}, 2 H{sub 2}O at 500 C for 24 hours in a current of oxygen leads to a cubic structure which is well-defined both in the bulk and superficially when x is less than 0.35. Above this atomic concentration of uranium, some uranium moves out of the lattice in the form of UO{sub 3} or U{sub 3}O{sub 8} according to the temperature. The mixed oxide is not stoichiometric,(U{sub x}Th{sub 1-x}O{sub 2+y}) and the average degree of oxidation of the uranium varies with the temperature and partial oxygen pressure. The oxides thus formed have a high surface area. By dissolving the mixed oxalates in a concentrated solution of ammonium oxalate, it is possible to deposit the catalyst on a support, but the differences in the solubilities of the thorium and uranium IV oxalates in the ammonium oxalate make it impossible to prepare double salts formed either of thorium and uranium and of ammonium. (author) [French] Nous avons etudie la decomposition thermique des oxalates d'uranyle et d'uranium IV en vue d'aboutir au dioxide d'uranium. Nous avons pu isoler les principales phases

Solubility Determination of Uranium (IV) Oxalates U(C{sub 2}O{sub 4}){sub 2}.6H{sub 2}O and M{sub 2}U{sub 2}(C{sub 2}O{sub 4}){sub 5}.nH{sub 2}O (M = mono-charged cation)

Energy Technology Data Exchange (ETDEWEB)

Costenoble, Sylvain; Grandjean, Stephane; Arab-Chapelet, Benedicte [CEA, Nuclear Energy Division, Radiochemistry and Process Department, Actinide Chemistry Laboratory, CEA Marcoule, bat 399, BP17171, 30207 Bagnols sur Ceze cedex (France); Abraham, Francis [UCCS - Solid Chemistry Unit, UMR CNRS 8181, ENSCL-USTL, B.P. 108, 59652 Villeneuve d' Ascq cedex (France)

2008-07-01

The solubility of uranium (IV) oxalate compounds was studied in order to have a precise insight of the behaviour of An(IV)-An(III) (An(IV) = U, Np or Pu and An(III) = Pu or Am) mixed oxalate in the context of oxalic co-conversion for actinide co-management. Concepts of thermodynamics of aqueous-solid solution are reviewed by introducing LIPPMANN theory and THORSTENSON and PLUMMER 'stoichiometric saturation' model in a way to understand and model the system of interest. Different analytical techniques have been developed in order to titrate uranium and/or other actinides at trace levels in solution. This thorough investigation is the basis of further experiments on the solubility of mixed U(IV)- An(III) oxalate solid solutions as a function of the nature of the trivalent actinide and the An(III)/U(IV) ratio. (authors)

Hot pressing of uranium nitride and mixed uranium plutonium nitride

International Nuclear Information System (INIS)

Chang, J.Y.

1975-01-01

The hot pressing characteristics of uranium nitride and mixed uranium plutonium nitride were studied. The utilization of computer programs together with the experimental technique developed in the present study may serve as a useful purpose of prediction and fabrication of advanced reactor fuel and other high temperature ceramic materials for the future. The densification of nitrides follow closely with a plastic flow theory expressed as: d rho/ dt = A/T(t) (1-rho) [1/1-(1-rho)/sup 2/3/ + B1n (1-rho)] The coefficients, A and B, were obtained from experiment and computer curve fitting. (8 figures) (U.S.)

Adaptable coordination of U(IV) in the 2D-(4,4) uranium oxalate network: From 8 to 10 coordinations in the uranium (IV) oxalate hydrates

International Nuclear Information System (INIS)

Duvieubourg-Garela, L.; Vigier, N.; Abraham, F.; Grandjean, S.

2008-01-01

Crystals of uranium (IV) oxalate hydrates, U(C 2 O 4 ) 2 .6H 2 O (1) and U(C 2 O 4 ) 2 .2H 2 O (2), were obtained by hydrothermal methods using two different U(IV) precursors, U 3 O 8 oxide and nitric U(IV) solution in presence of hydrazine to avoid oxidation of U(IV) into uranyl ion. Growth of crystals of solvated monohydrated uranium (IV) oxalate, U(C 2 O 4 ) 2 .H 2 O.(dma) (3), dma=dimethylamine, was achieved by slow diffusion of U(IV) into a gel containing oxalate ions. The three structures are built on a bi-dimensional complex polymer of U(IV) atoms connected through bis-bidentate oxalate ions forming [U(C 2 O 4 )] 4 pseudo-squares. The flexibility of this supramolecular arrangement allows modifications of the coordination number of the U(IV) atom which, starting from 8 in 1 increases to 9 in 3 and, finally increases, to 10 in 2. The coordination polyhedron changes from a distorted cube, formed by eight oxygen atoms of four oxalate ions, in 1, to a mono-capped square anti-prism in 3 and, finally, to a di-capped square anti-prism in 2, resulting from rotation of the oxalate ions and addition of one and two water oxygen atoms in the coordination of U(IV). In 1, the space between the ∞ 2 [U(C 2 O 4 ) 2 ] planar layers is occupied by non-coordinated water molecules; in 2, the space between the staggered ∞ 2 [U(C 2 O 4 ) 2 .2H 2 O] layers is empty, finally in 3, the solvate molecules occupy the interlayer space between corrugated ∞ 2 [U(C 2 O 4 ) 2 .H 2 O] sheets. The thermal decomposition of U(C 2 O 4 ) 2 .6H 2 O under air and argon atmospheres gives U 3 O 8 and UO 2 , respectively. - Graphical abstract: The adaptable environment of U(IV) in U(IV) oxalates: from eight cubic coordination in U(C 2 O 4 ) 2 .6H 2 O (a) completed by water oxygens to nine in [U(C 2 O 4 ) 2 .H 2 O](C 2 NH 5 ) (b) and ten coordination in U(C 2 O 4 ) 2 .2H 2 O (c)

Multiscale structural characterizations of mixed U(iv)-An(iii) oxalates (An(iii) = Pu or Am) combining XAS and XRD measurements.

Science.gov (United States)

Arab-Chapelet, B; Martin, P M; Costenoble, S; Delahaye, T; Scheinost, A C; Grandjean, S; Abraham, F

2016-04-28

Mixed actinide(III,IV) oxalates of the general formula M2.2UAn(C2O4)5·nH2O (An = Pu or Am and M = H3O(+) and N2H5(+)) have been quantitatively precipitated by oxalic precipitation in nitric acid medium (yield >99%). Thorough multiscale structural characterization using XRD and XAS measurements confirmed the existence of mixed actinide oxalate solid solutions. The XANES analysis confirmed that the oxidation states of the metallic cations, tetravalent for uranium and trivalent for plutonium and americium, are maintained during the precipitation step. EXAFS measurements show that the local environments around U(+IV), Pu(+III) and Am(+III) are comparable, and the actinides are surrounded by ten oxygen atoms from five bidentate oxalate anions. The mean metal-oxygen distances obtained by XAS measurements are in agreement with those calculated from XRD lattice parameters.

Mixing of Al into uranium silicides reactor fuels

International Nuclear Information System (INIS)

Ding, F.R.; Birtcher, R.C.; Kestel, B.J.; Baldo, P.M.

1996-11-01

SEM observations have shown that irradiation induced interaction of the aluminum cladding with uranium silicide reactor fuels strongly affects both fission gas and fuel swelling behaviors during fuel burn-up. The authors have used ion beam mixing, by 1.5 MeV Kr, to study this phenomena. RBS and the 27 Al(p, γ) 28 Si resonance nuclear reaction were used to measure radiation induced mixing of Al into U 3 Si and U 3 Si 2 after irradiation at 300 C. Initially U mixes into the Al layer and Al mixes into the U 3 Si. At a low dose, the Al layer is converted into UAl 4 type compound while near the interface the phase U(Al .93 Si .07 ) 3 grows. Under irradiation, Al diffuses out of the UAl 4 surface layer, and the lower density ternary, which is stable under irradiation, is the final product. Al mixing into U 3 Si 2 is slower than in U 3 Si, but after high dose irradiation the Al concentration extends much farther into the bulk. In both systems Al mixing and diffusion is controlled by phase formation and growth. The Al mixing rates into the two alloys are similar to that of Al into pure uranium where similar aluminide phases are formed

Comparison of open cycles of uranium and mixed oxides of thorium-uranium using advanced reactors

International Nuclear Information System (INIS)

Gonçalves, Letícia C.; Maiorino, José R.

2017-01-01

A comparative study of the mass balance and production costs of uranium oxide fuels was carried out for an AP1000 reactor and thorium-uranium mixed oxide in a reactor proposal using thorium called AP-Th1000. Assuming the input mass values for a fuel load the average enrichment for both reactors as well as their feed mass was determined. With these parameters, the costs were calculated in each fuel preparation process, assuming the prices provided by the World Nuclear Association. The total fuel costs for the two reactors were quantitatively compared with 18-month open cycle. Considering enrichment of 20% for the open cycle of mixed U-Th oxide fuel, the total uranium consumption of this option was 50% higher and the cost due to the enrichment was 70% higher. The results show that the use of U-Th mixed oxide fuels can be advantageous considering sustainability issues. In this case other parameters and conditions should be investigated, especially those related to fuel recycling, spent fuel storage and reduction of the amount of transuranic radioactive waste

Preparation, spectrometric analysis and determination of the electrochemical transport characteristics of uranium (IV) in aqueous systems

International Nuclear Information System (INIS)

Schwarzer, W.G.

1985-01-01

A process for the quantitative development of uranium-(IV) solutions in nitric and perchloric acid media was developed. After appropriate concentration setting of the solutions, the conductivity of the uranium (IV) in the dependence on concentration were analysed. The conversion of the measuring results on the standard system water was done by means of a conductivity theory; this allows a comparison with the conductivity data of other ions. The conductivity calculated, at an ion strength I tending to zero, provided the suitable data for the ion mobility and the transference number. (orig./PW) [de

Uranium(IV) adsorption by natural organic matter in anoxic sediments

Energy Technology Data Exchange (ETDEWEB)

Bone, Sharon E.; Dynes, James; Cliff, John B.; Barger, John

2017-01-09

Uranium is an important fuel source and a global environmental contaminant. It accumulates in the tetravalent state, U(IV), in anoxic sediments, including ore deposits, marine basins, and contaminated aquifers. However, very little is known about the speciation of U(IV) in low temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO₂) in anoxic sediments; yet studies now show that UO₂ is not often dominant in these environments. However, a model of U(IV) speciation under environmentally relevant conditions has not yet been developed. Here we show that complexes of U(IV) adsorb on organic carbon and organic carbon-coated clays in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that the U(IV) product depended on the reduction pathway, our results demonstrate that UO₂ formation can be inhibited simply by decreasing the U:solid ratio. Thus, it is the number and type of surface ligands that controls U(IV) speciation subsequent to U(VI) reduction. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider retention of U(IV) ions within the local sediment environment.

Multisensor system for determination of iron(II), iron(III), uranium(VI) and uranium(IV) in complex solutions

International Nuclear Information System (INIS)

Legin, A.V.; Seleznev, B.L.; Rudnitskaya, A.M.; Vlasov, Yu.G.; Tverdokhlebov, S.V.; Mack, B.; Abraham, A.; Arnold, T.; Baraniak, L.; Nitsche, H.

1999-01-01

Development and analytical evaluation of a multisensor system based on the principles of 'electronic tongue' for the determination of low contents of uranium(VI), uranium(IV), iron(II) and iron(III) in complex aqueous media have been carried out. A set of 29 different chemical sensors on the basis of all- solid-state crystalline and vitreous materials with enhanced electronic conductivity and redox and ionic cross-sensitivity have been incorporated into the sensor array. Multidimensional data have been processed by pattern recognition methods such as artificial neural networks and partial least squares. It has been demonstrated that Fe(II) and Fe(III) contents in the range from 10 -7 to 10 -4 mol L -1 of total iron concentration can be determined with the average precision of about 25 %. U(VI) and U(IV) contents can been determined with the average precision of 10-40% depending on the concentration. The developed multisensor system can be applied in future for the analysis of mining and borehole waters as well other contaminated natural media, including on-site measurements. (author)

Anaerobic U(IV) Bio-oxidation and the Resultant Remobilization of Uranium in Contaminated Sediments

International Nuclear Information System (INIS)

Coates, John D.

2005-01-01

A proposed strategy for the remediation of uranium (U) contaminated sites is based on immobilizing U by reducing the oxidized soluble U, U(VI), to form a reduced insoluble end product, U(IV). Due to the use of nitric acid in the processing of nuclear fuels, nitrate is often a co-contaminant found in many of the environments contaminated with uranium. Recent studies indicate that nitrate inhibits U(VI) reduction in sediment slurries. However, the mechanism responsible for the apparent inhibition of U(VI) reduction is unknown, i.e. preferential utilization of nitrate as an electron acceptor, direct biological oxidation of U(IV) coupled to nitrate reduction, and/or abiotic oxidation by intermediates of nitrate reduction. Recent studies indicates that direct biological oxidation of U(IV) coupled to nitrate reduction may exist in situ, however, to date no organisms have been identified that can grow by this metabolism. In an effort to evaluate the potential for nitrate-dependent bio-oxidation of U(IV) in anaerobic sedimentary environments, we have initiated the enumeration of nitrate-dependent U(IV) oxidizing bacteria. Sediments, soils, and groundwater from uranium (U) contaminated sites, including subsurface sediments from the NABIR Field Research Center (FRC), as well as uncontaminated sites, including subsurface sediments from the NABIR FRC and Longhorn Army Ammunition Plant, Texas, lake sediments, and agricultural field soil, sites served as the inoculum source. Enumeration of the nitrate-dependent U(IV) oxidizing microbial population in sedimentary environments by most probable number technique have revealed sedimentary microbial populations ranging from 9.3 x 101 - 2.4 x 103 cells (g sediment)-1 in both contaminated and uncontaminated sites. Interestingly uncontaminated subsurface sediments (NABIR FRC Background core FB618 and Longhorn Texas Core BH2-18) both harbored the most numerous nitrate-dependent U(IV) oxidizing population 2.4 x 103 cells (g sediment)-1

Heap bioleaching of uranium from low-grade granite-type ore by mixed acidophilic microbes

International Nuclear Information System (INIS)

Xuegang Wang; Zhongkui Zhou

2017-01-01

We evaluated uranium bioleaching from low-grade, granite-type uranium ore using mixed acidophilic microbes from uranium mine leachate. A 4854-ton plant-scale heap bioleaching process achieved sustained leaching with a uranium leaching efficiency of 88.3% using a pH of 1.0-2.0 and an Fe"3"+ dosage of 3.0-5.5 g/L. Acid consumption amounted to 25.8 g H_2SO_4 kg"-"1 ore. Uranium bioleaching follows a diffusion-controlled kinetic model with a correlation coefficient of 0.9136. Almost all uranium was dissolved in aqueous solution, except those encapsulated in quartz particles. Therefore, heap bioleaching by mixed acidophilic microbes enables efficient, economical, large-scale recovery of uranium from low-grade ores. (author)

Preparation of uranium-plutonium mixed nitride pellets with high purity

International Nuclear Information System (INIS)

Arai, Yasuo; Shiozawa, Ken-ichi; Ohmichi, Toshihiko

1992-01-01

Uranium-plutonium mixed nitride pellets have been prepared in the gloveboxes with high purity Ar gas atmosphere. Carbothermic reduction of the oxides in N 2 -H 2 mixed gas stream was adopted for synthesizing mixed nitride. Sintering was carried out in various conditions and the effect on the pellet characteristics was investigated. (author)

Kinetics and mechanism of the oxidation of uranium (IV) by hypochlorous acid in aqueous acidic perchlorate media

International Nuclear Information System (INIS)

Silverman, R.A.; Gordon, G.

1976-01-01

The oxidation of uranium(IV) by hypochlorous acid has been studied in aqueous sodium perchlorate--perchloric acid solutions. The reaction U 4 + + 2HOCl = UO 2 2 + + Cl 2 (aq) + 2H + proceeds appropriate to the rate law --d[U(IV)]/dt = k 0 . [U 4+ ][HOCl][H + ] -1 . At 25 0 and 3 M ionic strength, k 0 is 1.08 +- 0.07 sec -1 . Over the 1--25 0 temperature range, ΔH 2+ is 18.4 +- 0.1 kcal mole -1 , and ΔS 2+ is 3.1 +- 0.4 eu. The inverse hydrogen ion dependence of the rate law is explained by a rapid preequilibrium, in which a proton is lost from one of the reactants. A uranyl-like activated complex, [H 2 UO 2 Cl 3+ ] 2+ , is suggested, with one proton likely to be residing on each oxygen atom. Evidence is presented that the mechanism involves a two-electron transfer, with the intermediate chloride ion rapidly reacting with hypochlorous acid to form chlorine. The uranium(IV)-hypochlorous acid reaction plays an important role in the oxidation of uranium(IV) by aqueous chlorine solutions. The magnitude of this role was seriously underestimated by previous investigators

Investigation of the binding of tiron to uranium(IV) and uranium(VI) found in soil

International Nuclear Information System (INIS)

Birnbaum, E.R.; Iams, H.D.; del Rio Garcia, M.; Ford, D.K.; Smith, P.H.; Strietelmeier, B.; Brainard, J.

1993-01-01

The authors are investigating the utility of a chelate-reductant system to extract uranium from 2 million yards of contaminated soil at the Fernald uranium reprocessing plant near Cincinnati, Ohio. It has been found that reduction of the uranyl contaminants using Tiron as the ligand. Of concern is whether the increased mobilization is simply a result of the higher affinity of Tiron to U(IV), or whether reduction of amorphous iron oxides contained in the soil is exposing greater amounts of uranyl ions to the ligand. It is important to establish if the latter mechanism is occurring, since a removal process which does not damage the soil is desired. Potentiometric and spectrophotometric studies of Tiron binding to soluble uranyl and U(V) salts will be presented as models to help understand the soil studies. Extraction behavior of UO 2 (OH) 2 will also be presented

Determination of uranium and plutonium by sequential potentiometric titration

International Nuclear Information System (INIS)

Kato, Yoshiharu; Takahashi, Masao

1976-01-01

The determination of uranium and plutonium in mixed oxide fuels has been developed by sequential potentiometric titration. A weighed sample of uranium and plutonium oxides is dissolved in a mixture of nitric and hydrofluoric acids and the solution is fumed with sulfuric acid. After the reduction of uranium and plutonium to uranium(IV) and plutonium(III) by chromium(II) sulfate, 5 ml of buffer solution (KCl-HCl, pH 1.0) is added to the solution. Then the solution is diluted to 30 ml with water and the pH of the solution is adjusted to 1.0 -- 1.5 with 1 M sodium hydroxide. The solution is stirred until the oxidation of the excess of chromium(II) by air is completed. After the removal of dissolved oxygen by bubbling nitrogen through the solution for 10 minutes, uranium (IV) is titrated with 0.1 N cerium(IV) sulfate. Then, plutonium is titrated by 0.02 N cerium(IV) sulfate. When a mixture of uranium and plutonium is titrated with 0.1 N potassium dichromate potentiometrically, the potential change at the end point of plutonium is very small and the end point of uranium is also unclear when 0.1 N potassium permanganate is used as a titrant. In the present method, nitrate, fluoride and copper(II) interfere with the determination of plutonium and uranium. Iron interferes quantitatively with the determination of plutonium but not of uranium. Results obtained in applying the proposed method to 50 mg of mixtures of plutonium and uranium ((7.5 -- 50))% Pu were accurate to within 0.15 mg of each element. (auth.)

Determination of the oxygen-metal-ratio of uranium-americium mixed oxides

International Nuclear Information System (INIS)

Bartscher, W.

1982-01-01

During the dissolution of uranium-americium mixed oxides in phosphoric acid under nitrogen tetravalent uranium is oxidized by tetravalent americium. The obtained hexavalent uranium is determined by constant potential coulometry. The coulombs measured are equivalent to the oxygen in excess of the minimum composition of UO 2 x AmO 1 . 5 . The total uranium content of the sample is determined in a subsequent coulometric titration. The oxygen-metal ratio of the sample can be calculated for a given uranium-americium ratio. An excess of uranium dioxide is necessary in order to suppress the oxidation of water by tetravalent americium. The standard deviation of the method is 0.0017 O/M units. (orig.) [de

Peroxo complexes of molybdenum(VI), tungsten(VI), uranium(VI), zirconium(IV) and thorium(IV) ions containing tridentate Schiff bases derived from salicylaldehyde and amino acids

International Nuclear Information System (INIS)

Tarafder, M.T.H.; Khan, A.R.

1997-01-01

The synthesis of peroxo complexes of molybdenum(VI), tungsten(VI), uranium(VI), zirconium(IV), thorium(IV) and their possible oxygen transfer reactions is presented. An attempt has also been made to study the size of the metal ions and the electronic effect derived from the tridentate Schiff bases on the v 1 (O-O) mode of the complexes in their IR spectra

Seven-co-ordination in chlorohexakis(trimethylphosphine oxide)- uranium(IV) trichloride: crystal and molecular structure

Energy Technology Data Exchange (ETDEWEB)

Bombieri, G; Forsellini, E [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi; Brown, D; Whittaker, B

1976-01-01

The structure of the title compound has been determined by single-crystal X-ray diffraction methods from diffractometer data and refined to a final R of 0.023. The compound crystallises in space group R3c with asub(hex) = 18.447(3), csub(hex) = 19.348(3) A, Z = 6. The uranium atom is co-ordinated to one chlorine (U-Cl 2.813 A) and six oxygen atoms (mean U-O 2.26 A); the co-ordination polyhedron can be described as a distorted monocapped trigonal antiprism or as a distorted monocapped octahedron. The anionic chlorines are more than 6.22 A from the uranium atoms. The results are discussed in relation to spectral data for this and related uranium(IV) complexes.

Seven-co-ordination in chlorohexakis(trimethylphosphine oxide)- uranium(IV) trichloride: crystal and molecular structure

International Nuclear Information System (INIS)

Bombieri, G.; Forsellini, E.; Brown, D.; Whittaker, B.

1976-01-01

The structure of the title compound has been determined by single-crystal X-ray diffraction methods from diffractometer data and refined to a final R of 0.023. The compound crystallises in space group R3c with asub(hex) = 18.447(3), csub(hex) = 19.348(3) A, Z = 6. The uranium atom is co-ordinated to one chlorine (U-Cl 2.813 A) and six oxygen atoms (mean U-O 2.26 A); the co-ordination polyhedron can be described as a distorted monocapped trigonal antiprism or as a distorted monocapped octahedron. The anionic chlorines are more than 6.22 A from the uranium atoms. The results are discussed in relation to spectral data for this and related uranium(IV) complexes. (author)

Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings.

Science.gov (United States)

Wooles, Ashley J; Mills, David P; Tuna, Floriana; McInnes, Eric J L; Law, Gareth T W; Fuller, Adam J; Kremer, Felipe; Ridgway, Mark; Lewis, William; Gagliardi, Laura; Vlaisavljevich, Bess; Liddle, Stephen T

2018-05-29

Despite the fact that non-aqueous uranium chemistry is over 60 years old, most polarised-covalent uranium-element multiple bonds involve formal uranium oxidation states IV, V, and VI. The paucity of uranium(III) congeners is because, in common with metal-ligand multiple bonding generally, such linkages involve strongly donating, charge-loaded ligands that bind best to electron-poor metals and inherently promote disproportionation of uranium(III). Here, we report the synthesis of hexauranium-methanediide nanometre-scale rings. Combined experimental and computational studies suggest overall the presence of formal uranium(III) and (IV) ions, though electron delocalisation in this Kramers system cannot be definitively ruled out, and the resulting polarised-covalent U = C bonds are supported by iodide and δ-bonded arene bridges. The arenes provide reservoirs that accommodate charge, thus avoiding inter-electronic repulsion that would destabilise these low oxidation state metal-ligand multiple bonds. Using arenes as electronic buffers could constitute a general synthetic strategy by which to stabilise otherwise inherently unstable metal-ligand linkages.

Study of reactions between uranium-plutonium mixed oxide and uranium nitride and between uranium oxide and uranium nitride; Etude des reactions entre l`oxyde mixte d`uranium-plutonium et le nitrure d`uranium et entre l`oxyde d`uranium et le nitrure d`uranium

Energy Technology Data Exchange (ETDEWEB)

Lecraz, C

1993-06-11

A new type of combustible elements which is a mixture of uranium nitride and uranium-plutonium oxide could be used for Quick Neutrons Reactors. Three different studies have been made on the one hand on the reactions between uranium nitride (UN) and uranium-plutonium mixed oxide (U,Pu)O{sub 2}, on the other hand on these between UN and uranium oxide UO{sub 2}. They show a sizeable reaction between nitride and oxide for the studied temperatures range (1573 K to 1973 K). This reaction forms a oxynitride compound, MO{sub x} N{sub y} with M=U or M=(U,Pu), whose crystalline structure is similar to oxide`s. Solubility of nitride in both oxides is studied, as the reaction kinetics. (TEC). 32 refs., 48 figs., 22 tabs.

Facile reductive silylation of UO{sub 2}{sup 2+} to uranium(IV) chloride

Energy Technology Data Exchange (ETDEWEB)

Kiernicki, John J.; Bart, Suzanne C. [H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, IN (United States); Zeller, Matthias [H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, IN (United States); Department of Chemistry, Youngstown State University, Youngstown, OH (United States)

2017-01-19

General reductive silylation of the UO{sub 2}{sup 2+} cation occurs readily in a one-pot, two-step stoichiometric reaction at room temperature to form uranium(IV) siloxides. Addition of two equivalents of an alkylating reagent to UO{sub 2}X{sub 2}(L){sub 2} (X=Cl, Br, I, OTf; L=triphenylphosphine oxide, 2,2'-bipyridyl) followed by two equivalents of a silyl (pseudo)halide, R{sub 3}Si-X (R=aryl, alkyl, H; X=Cl, Br, I, OTf, SPh), cleanly affords (R{sub 3}SiO){sub 2}UX{sub 2}(L){sub 2} in high yields. Support is included for the key step in the process, reduction of U{sup VI} to U{sup V}. This procedure is applicable to a wide range of commercially available uranyl salts, silyl halides, and alkylating reagents. Under this protocol, one equivalent of SiCl{sub 4} or two equivalents of Me{sub 2}SiCl{sub 2} results in direct conversion of the uranyl to uranium(IV) tetrachloride. Full spectroscopic and structural characterization of the siloxide products is reported. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

A comparative study on determination of composition of uranium thorium mixed oxides by tube and radioisotope excited EDXRF

International Nuclear Information System (INIS)

Dhara, Sangita; Sanjay Kumar, S.; Misra, N.L.; Aggarwal, S.K.; Singh, Ajit Kumar; Lodha, G.S.

2009-01-01

Energy Dispersive X-ray Fluorescence (EDXRF) methods for determination of uranium and thorium in their mixed oxide matrices using tube and radioisotope excitation sources have been developed. The methodology involves preparation of mixed oxide calibration/sample mixtures of uranium and thorium oxides, mixing of fixed amount of internal standard Yttrium in form of Yttrium oxide, pelletizing these mixtures after thorough mixing and recording their EDXRF spectra using Rh target as well as 109 Cd radioisotope source. The samples were analysed for uranium and thorium on the basis of calibration plots

Characterization and uranium bioleaching performance of mixed iron- and sulfur-oxidizers versus iron-oxidizers

International Nuclear Information System (INIS)

Qian Li; Jing Sun; Dexin Ding; Qingliang Wang; Wenge Shi; Eming Hu; Xiaoyu Jiang; University of South China, Hengyang; Xingxing Wang

2017-01-01

In order to develop and apply mixed iron- and sulfur-oxidizers in uranium bioleaching, the characteristics of a mixed iron- and sulfur-oxidizing consortium (Consortium ISO) were comparatively investigated versus an iron-oxidizing consortium (Consortium IO). The results showed, the Consortium ISO exerted stronger oxidative ability and acid-producing ability than Consortium IO did. The synergy of sulfur-oxidizers and iron-oxidizers could change the structure and properties of the passivation substance, and work positively for eliminating the accumulation of passivation substance. In the bioleaching process, the uranium bioleaching experiments showed the recovery percentage of uranium reached 99.5% with Consortium ISO, 6.3% more than that of Consortium IO. (author)

Synthetic Strategies for the Synthesis of Ternary Uranium(IV) and Thorium(IV) Fluorides.

Science.gov (United States)

Klepov, Vladislav V; Felder, Justin B; Zur Loye, Hans-Conrad

2018-04-10

A series of new U(IV) and Th(IV) fluorides, Na 7 U 6 F 31 (1), NaUF 5 (2), NaU 2 F 9 (3), KTh 2 F 9 (4), NaTh 2 F 9 (5), (H 3 O)Th 3 F 13 (6), and (H 3 O)U 3 F 13 (7), was obtained using hydrothermal and low-temperature flux methods. Mild hydrothermal reactions with uranyl acetate as a precursor yielded 1, 7, and the monoclinic polymorph of NaU 2 F 9 , whereas direct reactions between UF 4 and NaF led to the formation of 2 and orthorhombic NaU 2 F 9 (3). This highlights an unexpected difference in reaction products when different starting uranium sources are used. All seven compounds were characterized by single-crystal X-ray diffraction, and their structures are compared on the basis of cation topology, revealing a close topological resemblance between fluorides on the basis of the layers observed in NaUF 5 (H 2 O). Phase-pure samples of 1, 2, and both polymorphs of NaU 2 F 9 were obtained, and their spectroscopic and magnetic properties were measured. The UV-vis data are dominated by the presence of U 4+ cations and agree well with the electronic transitions. Effective magnetic moments of the studied compounds were found to range from 3.08 to 3.59 μ B .

Method of preparation of uranium nitride

Science.gov (United States)

Kiplinger, Jaqueline Loetsch; Thomson, Robert Kenneth James

2013-07-09

Method for producing terminal uranium nitride complexes comprising providing a suitable starting material comprising uranium; oxidizing the starting material with a suitable oxidant to produce one or more uranium(IV)-azide complexes; and, sufficiently irradiating the uranium(IV)-azide complexes to produce the terminal uranium nitride complexes.

Uranium and plutonium distribution in unirradiated mixed oxide fuel from industrial fabrication

International Nuclear Information System (INIS)

Hanus, D.; Kleykamp, H.

1982-01-01

Different process variants developed in the last few years by the firm ALKEM to manufacture FBR and LWR mixed oxide fuel are given. The uranium and plutonium distribution is determined on the pellets manufactured with the help of the electron beam microprobe. The stepwise improvement of the uranium-plutonium homogeneity in the short-term developed granulate variants and in the long-term developed new processes are illustrated starting with early standard processes for FBR fuel. An almost uniform uranium-plutonium distribution could be achieved for the long-term developed new processes (OKOM, AuPuC). The uranium-plutonium homogeneity are quantified in the pellets manufactured according to the considered process variants with a newly defined quality number. (orig.)

The development of the production process for the thorium/uranium dicarbide fuel kernels for the first charge of the Dragon Reactor

International Nuclear Information System (INIS)

Burnett, R.C.; Hankart, L.J.; Horsley, G.W.

1965-05-01

The development of methods of producing spheroidal sintered porous kernels of hyperstoichiometric thorium/uranium dicarbide solid solution from thorium/uranium monocarbide/carbon and thoria/urania/carbon powder mixes is described. The work has involved study of (i) Methods of preparing green kernels from UC/Th/C powder mixes using the rotary sieve technique. (ii) Methods of producing green kernels from UO2/Th02/C powder mixes using the planetary mill technique. (iii) The conversion by appropriate heat treatment of green kernels produced by both routes to sintered porous kernels of thorium/uranium carbide. (iv) The efficiency of the processes. (author)

Phospholyl-uranium complexes

International Nuclear Information System (INIS)

Gradoz, Philippe

1993-01-01

After having reported a bibliographical study on penta-methylcyclopentadienyl uranium complexes, and a description of the synthesis and radioactivity of uranium (III) and (IV) boron hydrides compounds, this research thesis reports the study of mono and bis-tetramethyl-phospholyl uranium complexes comprising chloride, boron hydride, alkyl and alkoxide ligands. The third part reports the comparison of structures, stabilities and reactions of homologue complexes in penta-methylcyclopentadienyl and tetramethyl-phospholyl series. The last part addresses the synthesis of tris-phospholyl uranium (III) and (IV) complexes. [fr

Gravimetric determination of uranium(VI) and thorium(IV) with substituted pyrazolones

International Nuclear Information System (INIS)

Arora, H.C.; Rao, G.N.

1981-01-01

4-Acylpyrazolones like 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP), 1-phenyl-3-methyl-4-p-nitrobenzoyl-5-pyrazolone (PMNP) and 1-phenyl-3-methyl-4-(3,5 dinitrobenzoyl)-5-pyrazolone (PMDP) have been synthesized and developed as gravimetric reagents for the determination of U(VI) and Th(IV). Uranium(VI) is almost quantitatively precipitated with PMBP, PMNP, and PMDP at pH 2.20, 1.85 and 1.70 respectively. The pH values for the complete precipitation of thorium(IV) with PMBP, PMNP and PMDP are 2.90, 2.75 and 2.50 respectively. PMBP has proved to be an efficient ligand for gravimetric determination of U(VI) by direct weighing method after drying at 100 +- 10 deg C. The percentage relative error varies from 0.4 to 1.6 in the determination of U(VI) by this method. The effect of a number of interfering ions on the precipitation of U(VI) by PMBP has been reported. (author)

Simultaneous precipitation of carbonato complexes of uranium and plutonium with cationic surfactants

International Nuclear Information System (INIS)

Heckmann, K.; Strnad, J.; Huber, K.

1992-01-01

The proposed method allows to separate Uranium, Thorium and Cerium from carbonate solutions and the further processing of these metals to mixed oxides. The separation can be divided into three steps: 1. Precipitation of the metals with a 10-fold surplus of carbonate and a 5-fold surplus of a cationic surfactant. 2. Thermal decomposition of the precipitates in air at 600 C. 3. Reduction of U(VI) to U(IV) with CO at 500 C. Mixed oxides in any ratio are formed in this way. This is possible due to the coprecipitation of both metals. Comparing the standard potentials it is clear that Ce(IV) is more easily reduced that Pu(IV). Therefore, the chance on the formation of U/Pu mixed oxides by this method is quite good. (orig.) [de

Soiled-based uranium disequilibrium and mixed uranium-thorium series radionuclide reference materials

International Nuclear Information System (INIS)

Donivan, S.; Chessmore, R.

1988-12-01

The US Department of Energy (DOE) Office of Remedial Action and Waste Technology has assigned the Technical Measurements Center (TMC), located at the DOE Grand Junction Colorado, Projects Office and operated by UNC Geotech (UNC), the task of supporting ongoing remedial action programs by providing both technical guidance and assistance in making the various measurements required in all phases of remedial action work. Pursuant to this task, the Technical Measurements Center prepared two sets of radionuclide reference materials for use by remedial action contractors and cognizant federal and state agencies. A total of six reference materials, two sets comprising three reference materials each, were prepared with varying concentrations of radionuclides using mill tailings materials, ores, and a river-bottom soil diluent. One set (disequilibrium set) contains varying amounts of uranium with nominal amounts of radium-226. The other set (mixed-nuclide set) contains varying amounts of uranium-238 and thorium-232 decay series nuclides. 14 refs., 10 tabs

Behaviour of uranium during mixing in the Delaware and Chesapeake estuaries

International Nuclear Information System (INIS)

Sarin, M.M.; Church, T.M.

1994-01-01

Unequivocal evidence is presented for the removal of uranium in two major estuarine systems of the north-eastern United States: the Delaware and Chesapeake Bays. In both the estuaries, during all seasons but mostly in summer, dissolved uranium shows distinctly non-conservative behaviour at salinities ≤ 5. At salinities above 5, there are no deviations from the ideal dilution line. In these two estuaries as much as 22% of dissolved uranium is removed at low salinities, around salinity 2. This pronounced removal of uranium observed at low salinities has been investigated in terms of other chemical properties measured in the Delaware Estuary. In the zone of uranium removal, dissolved oxygen is significantly depleted and pH goes through a minimum down to 6.8. In the same low salinity regime, total alkalinity shows negative deviation from the linear dilution line and phosphate is removed. Humic acids, dissolved iron and manganese are also rapidly removed during estuarine mixing in this low salinity region. Thus, it appears that removal of uranium is most likely related to those properties of alkalinity and acid-base system of the upper estuary that may destabilize the uranium-carbonate complex. Under these conditions, uranium may associate strongly with phosphates or humic substances and be removed onto particulate phases and deposited within upper estuarine sediments. (author)

Plutonium oxides and uranium and plutonium mixed oxides. Carbon determination

International Nuclear Information System (INIS)

Anon.

Determination of carbon in plutonium oxides and uranium plutonium mixed oxides, suitable for a carbon content between 20 to 3000 ppm. The sample is roasted in oxygen at 1200 0 C, the carbon dioxide produced by combustion is neutralized by barium hydroxide generated automatically by coulometry [fr

Studies on the absorption of uranium and plutonium on macroporous anion-exchange resins from mixed solvent media

International Nuclear Information System (INIS)

Chetty, K.V.; Mapara, P.M.; Godbole, A.G.; Swarup, Rajendra

1995-01-01

The ion-exchange studies on uranium and plutonium using macroporous anion-exchange resins from an aqueous-organic solvent mixed media were carried out to develop a method for their separation. Out of the several water miscible organic solvents tried, methanol and acetone were found to be best suited. Distribution data for U(VI) and Pu(IV) for three macroporous resins Tulsion A-27(MP) (strong base), Amberlyst A-26(MP) (strong base) and Amberlite XE-270(MP) (weak base) as a function of (i) nitric acid concentration (ii) organic solvent concentration were obtained. Based on the data separation factors for Pu/U were calculated. Column experiments using Tulsion A-27(MP) from a synthetic feed (HNO 3 - methanol and HNO 3 - acetone) containing Pu and U in different ratios were carried out. Plutonium was recovered from the bulk of the actual solution generated during the dissolution of plutonium bearing fuels. The method has the advantage of loading plutonium from as low as 1M nitric acid in presence of methanol or acetone and could be used satisfactorily for its recovery from solutions containing plutonium and uranium. (author). 11 refs., 4 figs., 16 tabs

Catechol functionalized aminopropyl silica gel: synthesis, characterization and preconcentrative separation of uranium(VI) from thorium(IV)

International Nuclear Information System (INIS)

Metilda, P.; Mary Gladis, J.; Prasada Rao, T.P.

2005-01-01

A novel solid phase extractant is prepared by chemically immobilizing catechol with diazotized aminopropyl silica gel. The resulting catechol functionalized silica gel (CASG) was characterized by FTIR, and microanalysis and was used for selective enrichment of uranium(VI) from other inorganic ions. The optimum pH range for maximum sorption of uranium(VI) and thorium(IV) was found to be in the range 3.5-6.0. The above actinides were eluted with 10 cm 3 of 1.0 mol dm -3 HCl and determined by using an Arsenazo III spectrophotometric procedure. The calibration graph was rectilinear over the uranium(VI) concentration in the range 2-100 μg dm -3 with a relative standard deviation of 2.15% (for 25 μg of uranium(VI) present in 1.0 dm 3 of sample). The validation of the developed preconcentration procedure was carried out by analyzing marine sediment (MESS-3, NRC, Canada) and soil (IAEA soil-7, Austria) reference materials. The developed preconcentration method enables a simple instruments like a spectrophotometer gave comparable values of uranium(VI) to that of standard inductively coupled plasma-mass spectrometric values during the analysis of real soil and sediment samples. (orig.)

White paper on possible inclusion of mixed plutonium-uranium oxides in DOE-STD-3013-96

International Nuclear Information System (INIS)

Haschke, J.M.; Venetz, T.; Szempruch, R.; McClard, J.W.

1997-11-01

This report assesses stabilization issues concerning mixed plutonium-uranium oxides containing 50 mass % Pu. Possible consequences of uranium substitution on thermal stabilization, specific surface areas, moisture readsorption behavior, loss-on-ignition analysis, and criticality safety of the oxide are examined and discussed

Thorium/uranium mixed oxide nano-crystals: Synthesis, structural characterization and magnetic properties

International Nuclear Information System (INIS)

Hudry, Damien; Griveau, Jean-Christophe; Apostolidis, Christos; Colineau, Eric; Rasmussen, Gert; Walter, Olaf; Wang, Di; Venkata Sai Kiran Chakravadhaluna; Courtois, Eglantine; Kubel, Christian

2014-01-01

One of the primary aims of the actinide community within nano-science is to develop a good understanding similar to what is currently the case for stable elements. As a consequence, efficient, reliable and versatile synthesis techniques dedicated to the formation of new actinide-based nano-objects (e.g., nano-crystals) are necessary. Hence, a 'library' dedicated to the preparation of various actinide based nano-scale building blocks is currently being developed. Nano-scale building blocks with tunable sizes, shapes and compositions are of prime importance. So far, the non-aqueous synthesis method in highly coordinating organic media is the only approach which has demonstrated the capability to provide size and shape control of actinide-based nano-crystals (both for thorium and uranium, and recently extended to neptunium and plutonium). In this paper, we demonstrate that the non-aqueous approach is also well adapted to control the chemical composition of the nano-crystals obtained when mixing two different actinides. Indeed, the controlled hot co-injection of thorium acetylacetonate and uranyl acetate (together with additional capping agents) into benzyl ether can be used to synthesize thorium/uranium mixed oxide nano-crystals covering the full compositional spectrum. Additionally, we found that both size and shape are modified as a function of the thorium/uranium ratio. Finally, the magnetic properties of the different thorium/uranium mixed oxide nano-crystals were investigated. Contrary to several reports, we did not observe any ferromagnetic behavior. As a consequence, ferromagnetism cannot be described as a universal feature of nano-crystals of non-magnetic oxides as recently claimed in the literature. (authors)

Hexacoordinated mixed-ligand complexes of vanadium(IV) and copper(II)

International Nuclear Information System (INIS)

Islam, M.S.; Motahera Begum; Roy, H.N.; Haroon, S.A.Q.M.

1996-01-01

The literature reports simple complexes of metal ions with Schiff bases derived from amino acids. But their mixed-ligand complexes are very rare. Keeping this fact in mind, some new mixed ligand complexes of V IV and Cu II with tridentate Schiff bases derived from glycine, salicylaldehyde and amino bases, e.g. quinoline (Q), isoquinoline (IQ), 2-picoline (2-pic), 4-picoline (4-pic) and pyridine (Py) were prepared and studied. 6 refs., 1 tab

Catechol functionalized aminopropyl silica gel: synthesis, characterization and preconcentrative separation of uranium(VI) from thorium(IV)

Energy Technology Data Exchange (ETDEWEB)

Metilda, P.; Mary Gladis, J.; Prasada Rao, T.P. [Regional Research Lab. (CSIR), Trivandrum (India)

2005-07-01

A novel solid phase extractant is prepared by chemically immobilizing catechol with diazotized aminopropyl silica gel. The resulting catechol functionalized silica gel (CASG) was characterized by FTIR, and microanalysis and was used for selective enrichment of uranium(VI) from other inorganic ions. The optimum pH range for maximum sorption of uranium(VI) and thorium(IV) was found to be in the range 3.5-6.0. The above actinides were eluted with 10 cm{sup 3} of 1.0 mol dm{sup -3} HCl and determined by using an Arsenazo III spectrophotometric procedure. The calibration graph was rectilinear over the uranium(VI) concentration in the range 2-100 {mu}g dm{sup -3} with a relative standard deviation of 2.15% (for 25 {mu}g of uranium(VI) present in 1.0 dm{sup 3} of sample). The validation of the developed preconcentration procedure was carried out by analyzing marine sediment (MESS-3, NRC, Canada) and soil (IAEA soil-7, Austria) reference materials. The developed preconcentration method enables a simple instruments like a spectrophotometer gave comparable values of uranium(VI) to that of standard inductively coupled plasma-mass spectrometric values during the analysis of real soil and sediment samples. (orig.)

Synthesis and structure determination of a stable organometallic uranium(V) imine complex and its isolobal anionic U(IV)-ate complex

Energy Technology Data Exchange (ETDEWEB)

Sharma, M.; Botoshanskii, M.; Eisen, M.S. [Schulich Faculty of Chemistry, and Institute of Catalysis Science and Technology, Technion Israel Institute of Technology, Haifa (Israel); Bannenberg, Th.; Tamm, M. [Institut fur Anorganische und Analytische Chemie, Technische Universitat Braunschweig (Germany)

2010-06-15

The reaction of one equivalent of Cp*{sub 2}UCl{sub 2} with 2-(trimethylsilyl-imino)-1,3-di-tert-butyl-imidazoline in boiling toluene afforded a one electron oxidation of the uranium metal and the opening of the N-heterocyclic ring, resulting in the formation of an organometallic uranium(V) imine complex. This complex crystallized with one molecule of toluene in the unit cell, and its solid-state structure was determined by X-ray diffraction analysis. When the same reaction was performed in perdeuterated toluene, a myriad of organometallic complexes were obtained, however, when equimolar amounts of water were used in toluene, the same complex was obtained, and its solid state characterization shows two independent molecules in the unit cell with an additional water molecule. For comparison of the geometric parameters, the corresponding isolobal anionic uranium(IV) complex [Cp*{sub 2}UCl{sub 3}]{sup -} was synthesized by the reaction of Cp*{sub 2}UCl{sub 2} with 1,3-di-tert-butyl-imidazolium chloride, and the resulting U(IV)-ate complex was characterized by X-ray diffraction analysis. (authors)

Studies of the effects of organic materials on the sorption of uranium(IV) and thorium(IV) on London clay and Caithness flagstones

International Nuclear Information System (INIS)

Baston, G.M.N.; Berry, J.A.; Bond, K.A.; Brownsword, M.; Linklater, C.M.

1991-08-01

The effects of the presence of cellulosic degradation products on the sorption of uranium (IV) and thorium(IV) on London clay and Caithness flagstones have been studied using the batch sorption method. Experimental conditions were chosen to simulate both those expected close to a cementitious repository (pH ∼11) and at the edge of the zone of migration of the alkaline plume (pH ∼ 8). Work was carried out (i) under baseline conditions, in the absence of organic materials; (ii) with 2 x 10 -3 M gluconate, acting as a well-characterised degradation product simulant; (iii) with authentic degradation products. The results show that the presence of authentic degradation products has a small effect on sorption and the presence of gluconate at a high concentration has a marked impact. (author)

Studies of the effects of organic materials on the sorption of uranium(IV) and thorium(IV) on London clay and Caithness flagstones

Energy Technology Data Exchange (ETDEWEB)

Baston, G.M.N.; Berry, J.A.; Bond, K.A.; Brownsword, M.; Linklater, C.M.

1991-08-01

The effects of the presence of cellulosic degradation products on the sorption of uranium (IV) and thorium(IV) on London clay and Caithness flagstones have been studied using the batch sorption method. Experimental conditions were chosen to simulate both those expected close to a cementitious repository (pH {approx}11) and at the edge of the zone of migration of the alkaline plume (pH {approx} 8). Work was carried out (i) under baseline conditions, in the absence of organic materials; (ii) with 2 x 10{sup -3}M gluconate, acting as a well-characterised degradation product simulant; (iii) with authentic degradation products. The results show that the presence of authentic degradation products has a small effect on sorption and the presence of gluconate at a high concentration has a marked impact. (author).

Persistent U(IV) and U(VI) following in-situ recovery (ISR) mining of a sandstone uranium deposit, Wyoming, USA

Science.gov (United States)

Gallegos, Tanya J.; Campbell, Kate M.; Zielinski, Robert A.; Reimus, P.W.; J.T. Clay,; N. Janot,; J. J. Bargar,; Benzel, William M.

2015-01-01

Drill-core samples from a sandstone-hosted uranium (U) deposit in Wyoming were characterized to determine the abundance and distribution of uranium following in-situ recovery (ISR) mining with oxygen- and carbon dioxide-enriched water. Concentrations of uranium, collected from ten depth intervals, ranged from 5 to 1920 ppm. A composite sample contained 750 ppm uranium with an average oxidation state of 54% U(VI) and 46% U(IV). Scanning electron microscopy (SEM) indicated rare high uranium (∼1000 ppm U) in spatial association with P/Ca and Si/O attributed to relict uranium minerals, possibly coffinite, uraninite, and autunite, trapped within low permeability layers bypassed during ISR mining. Fission track analysis revealed lower but still elevated concentrations of U in the clay/silica matrix and organic matter (several 10 s ppm) and yet higher concentrations associated with Fe-rich/S-poor sites, likely iron oxides, on altered chlorite or euhedral pyrite surfaces (but not on framboidal pyrite). Organic C (mining, the likely sequestration of uranium within labile iron oxides following mining and sensitivity to changes in redox conditions requires careful attention during groundwater restoration.

Reactivity of the uranium (U(IV)/U(VI)) and the plutonium (Pu(III)/Pu(IV)) in nitric aqueous solution under ultrasound

International Nuclear Information System (INIS)

Venault, L.

1998-01-01

To minimize the volumes of solid waste and industrial effluents generated at the end of cycle, particularly in the spent nuclear fuel reprocessing industry, research is currently under way on so-called innovative processes, designed to induce chemical reactions without adding reagent to the media. Among these processes, the use of ultrasound can prove advantageous, and the purpose of this study is to assess accurately the potential for its application. In the present context, this work shows that the transmission of an ultrasonic wave in aqueous nitric acid solution leads to: the accumulation of nitrous acid in solution, until a steady-sate concentration is reached; the removal of nitrogen monoxide and nitrogen dioxide in the gas stream. The initial kinetics of the formation of HNO 2 in solution was quantified as a function of the nitric acid concentration and the ultrasound intensity. It was also shown than an excess of nitrous acid in nitric solution decomposes under the effect of ultrasound. It is also possible to accumulate hydrogen peroxide in solution during the ultrasonic irradiation of aqueous nitric acid solutions in the presence of a chemical species N 2 H 5 + , NH 2 SO 3 H...) which reacts rapidly with HNO 2 , preventing the reduction of H 2 O 2 by HNO 2 . The mechanisms of HNO 2 formation and decomposition, and the mechanism of H 2 O 2 formation during the ultrasonic irradiation of aqueous nitric acid solutions, are presented. Control of H 2 O 2 or HNO 2 in a nitric acid medium under the effect of an ultrasonic wave can be exploited to control redox reactions of uranium and plutonium ions, particularly with respect to the oxidation of U and Pu (U(IV)→ U(IV) or Pu(III) → Pu(IV)) and the reduction of Pu (Pu(IV)→ Pu(III). The redox behavior of uranium and plutonium ions in aqueous nitric solution subject to an ultrasonic flux is interpreted in term of effects induced on the reaction medium, and reveals the potential for using ultrasound to cause

Solvent extraction of hafnium(IV) by dinonylnaphthalene sulfonic acid from mixed aqueous-organic media

International Nuclear Information System (INIS)

Hala, J.; Piperkovova, H.

1979-01-01

The extraction of hafnium(IV) by heptane and toluene solutions of dinonylnaphthalene sulfonic acid (HD) from mixed aqueous-organic solutions has been studied. Alcohols, ketones, carboxylic acids, cyclic ethers, dimethylsulfoxide and dimethylformamide were used as the organic component of the mixed phase. Methanol, ethanol, formic acid and dioxane increased the extractability of Hf(IV) whereas other solvents showed only an antagonistic effect. The results were discussed from the point of view of the changes in micellar structure of HD, and compared with the uptake of Hf(IV) by resinous cation exchangers. The solubilization by HD of alcohols, carboxylic acids and dimethylsulfoxide was demonstrated by using the corresponding 14 C and 35 S labelled compounds. (author)

Reactivity of the uranium (U(IV)/U(VI)) and the plutonium (Pu(III)/Pu(IV)) in nitric aqueous solution under ultrasound; De l'influence des ultrasons sur la reactivite de l'uranium (U(IV)/U(VI)) et du plutonium (PU(III)/PU(IV)) en solution aqueuse nitrique

Energy Technology Data Exchange (ETDEWEB)

Venault, L

1998-07-01

To minimize the volumes of solid waste and industrial effluents generated at the end of cycle, particularly in the spent nuclear fuel reprocessing industry, research is currently under way on so-called innovative processes, designed to induce chemical reactions without adding reagent to the media. Among these processes, the use of ultrasound can prove advantageous, and the purpose of this study is to assess accurately the potential for its application. In the present context, this work shows that the transmission of an ultrasonic wave in aqueous nitric acid solution leads to: the accumulation of nitrous acid in solution, until a steady-sate concentration is reached; the removal of nitrogen monoxide and nitrogen dioxide in the gas stream. The initial kinetics of the formation of HNO{sub 2} in solution was quantified as a function of the nitric acid concentration and the ultrasound intensity. It was also shown than an excess of nitrous acid in nitric solution decomposes under the effect of ultrasound. It is also possible to accumulate hydrogen peroxide in solution during the ultrasonic irradiation of aqueous nitric acid solutions in the presence of a chemical species (N{sub 2}H{sub 5}{sup +}, NH{sub 2}SO{sub 3}H...) which reacts rapidly with HNO{sub 2}, preventing the reduction of H{sub 2}O{sub 2} by HNO{sub 2}. The mechanisms of HNO{sub 2} formation and decomposition, and the mechanism of H{sub 2}O{sub 2} formation during the ultrasonic irradiation of aqueous nitric acid solutions, are presented. Control of H{sub 2}O{sub 2} or HNO{sub 2} in a nitric acid medium under the effect of an ultrasonic wave can be exploited to control redox reactions of uranium and plutonium ions, particularly with respect to the oxidation of U and Pu (U(IV){yields} U(IV) or Pu(III) {yields} Pu(IV)) and the reduction of Pu (Pu(IV){yields} Pu(III). The redox behavior of uranium and plutonium ions in aqueous nitric solution subject to an ultrasonic flux is interpreted in term of effects

Thiocyanato species of uranium(IV)

International Nuclear Information System (INIS)

Loyson, P.L.R.

1974-12-01

The aim of this thesis was to study the system U +4 /ClO 4 - /NCS - /HMPA/ - Solvent. This was done by means of various physical chemical methods. Spectrophotometric and conductometric evidence indicated that the following are the important species, which exist in acetone solution: (U(ClO 4 ) 3 .3acetone) + , (U(NCS) 3 .5acetone) + , (U 2 (NCS) 9 .6acetone) - , (U(NCS) 3 .2HMPA.3acetone) + , (U(NCS) 5 .2HMPA) - , (U(ClO 4 ) 3 .3HMPA) + , (U(NCS).5HMPA) +3 , (U(NCS) 2 .4HMPA) +2 and (U(NCS) 3 .3HMPA) + . The replacement of the large ClO 4 - ion by the much smaller NCS - anion results in a change in coordination of the U +4 , from six to eight. The formation of the species (U(NCS) 5 .2HMPA) - wasalso suggested by infrared studies and solubility determinations. The effect of a polar solvent on U(NCS) 4 .4HMPA was also studied, which indicated that, on solvation in methyl cyanide, U(NCS) 4 .4HMPA loses bound HMPA molecules. The ultimate goal of this project, i.e. the determination of the successive stability constants of the uranium(IV)thiocyanato complexes in acetone, was not reached, however, due to limitations of the computer program used. A qualitative treatment revealed that the stability of (U(NCS) 3 .5acetone) + , in acetone, is of the same order of magnitude as that of Co(NCS) 3 - ; similarly the species (U 2 (NCS) 9 .6acetone) - seems to be as stable as C0(NCS) 4 =. It was also indicated that excess U +4 cannot remove all bound NCS - from Co +2 . Finally the thiocyanato complexes of U +4 , relative to those of CO +2 , seem to be more stable in methyl cyanide, a N-donor solvent, than in acetone, an O-donor solvent

Cyclopentadienyl uranium, neptunium and plutonium chemistry

International Nuclear Information System (INIS)

Plews, M.J.

1985-01-01

The thesis presents the preparation and characterisation of a number of mono, bis and tris(cyclopentadienyl) complexes of uranium(IV), neptunium(IV) and plutonium(IV). The work of previous studies on mono(cyclopentadienyl) thorium and uranium complexes has been extended, and a range of isostructural neptunium species isolated. Their mode of formation and stability in tetrahydrofuran and acetonitrile solutions was investigated. (author)

Effect of cooling rate on achieving thermodynamic equilibrium in uranium-plutonium mixed oxides

Science.gov (United States)

Vauchy, Romain; Belin, Renaud C.; Robisson, Anne-Charlotte; Hodaj, Fiqiri

2016-02-01

In situ X-ray diffraction was used to study the structural changes occurring in uranium-plutonium mixed oxides U1-yPuyO2-x with y = 0.15; 0.28 and 0.45 during cooling from 1773 K to room-temperature under He + 5% H2 atmosphere. We compare the fastest and slowest cooling rates allowed by our apparatus i.e. 2 K s-1 and 0.005 K s-1, respectively. The promptly cooled samples evidenced a phase separation whereas samples cooled slowly did not due to their complete oxidation in contact with the atmosphere during cooling. Besides the composition of the annealing gas mixture, the cooling rate plays a major role on the control of the Oxygen/Metal ratio (O/M) and then on the crystallographic properties of the U1-yPuyO2-x uranium-plutonium mixed oxides.

Thermal expansion studies on uranium-neodymium mixed oxide solid solutions

International Nuclear Information System (INIS)

Panneerselvam, G.; Venkata Krishnan, R.; Antony, M.P.; Nagarajan, K.

2012-01-01

Uranium-Neodymium mixed oxides solid solutions (U 1-y Nd y ) O 2 (y=0.2-0.95) were prepared by combustion synthesis using citric acid as fuel. Structural characterization and computation of lattice parameter was carried out from room temperature X-ray diffraction measurements. Single-phase fluorite structure was observed up to y=0.80. For solid solutions with y>0.80 additional Nd 2 O 3 lines were visible

Synthesis and studies of some organometallic compounds of uranium IV

International Nuclear Information System (INIS)

Marquet-Ellis, Hubert; Folcher, Gerard.

1975-06-01

The organometallic compounds of uranium IV have been well known for a long-time but some difficulties in the synthese subsist. The procedures and the apparatus allowing to obtain these compounds with good yields are described. The cyclopenta dienyl compounds U(C 5 H 5 ) 3 Cl, U(C 5 H 5 ) 4 are prepared by reaction of UCl 4 with Na(C 5 H 5 ) in tetrahydrofurane. The cyclooctatetraene compound U(C 8 H 8 ) 2 ''Uranocene'' is obtained by reaction of K 2 (C 8 H 8 ) on UCl 4 in tetrahydrofurane. The NMR spectrum of the solution during the reaction shows the appearance of the product. These compounds have been identified by chemical analysis and X rays. The visible spectra of U(C 5 H 5 ) 2 Cl and U(C 8 H 8 ) 2 in gaseous phase have been obtained [fr

Grain growth kinetics in uranium-plutonium mixed oxides

International Nuclear Information System (INIS)

Sari, C.

1986-01-01

Grain growth rates were investigated in uranium-plutonium mixed oxide specimens with oxygen-to-metal ratios 1.97 and 2.0. The specimens in the form of cylindrical pellets were heated in a temperature gradient similar to that existing in a fast reactor. The results are in agreement with the cubic rate law. The mean grain size D(μm) after annealing for time t (min) is represented by D 3 -D 0 3 =1.11x10 12 . exp(-445870/RT).t and D 3 -D 0 3 =2.55x10 9 .exp(-319240/RT).t for specimens with overall oxygen-to-metal ratios 1.97 and 2.0, respectively (activation energies expressed in J/mol). An example for the influence of the oxygen-to-metal ratio on the grain growth in mixed oxide fuel during operation in a fast reactor is also given. (orig.)

U(IV) chalcogenolates synthesized via oxidation of uranium metal by dichalcogenides.

Science.gov (United States)

Gaunt, Andrew J; Scott, Brian L; Neu, Mary P

2006-09-04

Treatment of uranium metal with dichalcogenides in the presence of a catalytic amount of iodine in pyridine affords molecular U(IV) chalcogenolates that do not require stabilizing ancillary ligands. Oxidation of U(0) by PhEEPh yields monomeric seven-coordinate U(EPh)4(py)3 (E = S(1), Se(2)). The dimeric eight-coordinate complexes [U(EPh)2(mu2-EPh)2(CH3CN)2]2 (E = S(3), Se(4)) are obtained by crystallization from solutions of 1 and 2 dissolved in acetonitrile. Oxidation of U(0) by pySSpy and crystallization from thf yields nine-coordinate U(Spy)4(thf) (5). Incorporation of elemental selenium into the oxidation of U(0) by PhSeSePh results in the isolation of [U(py)2(SePh)(mu3-Se)(mu2-SePh)]4.4py (6), a tetrameric cluster in which each U(IV) ion is eight-coordinate and the U4Se4 core forms a distorted cube. The compounds were analyzed spectroscopically and the single-crystal X-ray structures of 1 and 3-6 were determined. The isolation of 1-6 represents six new examples of actinide chalcogenolates and allows insight into the nature of "hard" actinide ion-"soft" chalcogen donor interactions.

Uranium control in phosphogypsum

International Nuclear Information System (INIS)

Hurst, F.J.; Arnold, W.D.

1980-01-01

In wet-process phosphoric acid plants, both previous and recent test results show that uranium dissolution from phosphate rock is significantly higher when the rock is acidulated under oxidizing conditions than under reducing conditions. Excess sulfate and excess fluoride further enhance the distribution of uranium to the cake. Apparently the U(IV) present in the crystal lattice of the apatite plus that formed by reduction of U(IV) by FE(II) during acidulation is trapped or carried into the crystal lattice of the calcium sulfate crystals as they form and grow. The amount of uranium that distributes to hemihydrate filter cake is up to seven times higher than the amount that distributes to the dihydrate cake. About 60% of the uranium in hemihydrate cakes can be readily leached after hydration of the cake, but the residual uranium (20 to 30%) is very difficult to remove economically. Much additional research is needed to develop methods for minimizing uranium losses to calcium filter cakes

Titrimetric determination of uranium

International Nuclear Information System (INIS)

Florence, T.M.

1989-01-01

Titrimetric methods are almost invariably used for the high precision assay of uranium compounds, because gravimetric methods are nonselective, and not as reliable. Although precipitation titrations have been used, for example with cupferron and ferrocyanide, and chelate titrations with EDTA and oxine give reasonable results, in practice only redox titrations find routine use. With all redox titration methods for uranium a precision of 01 to 02 percent can be achieved, and precisions as high as 0.003 percent have been claimed for the more refined techniques. There are two types of redox titrations for uranium in common use. The first involves the direct titration of uranium (VI) to uranium (IV) with a standard solution of a strong reductant, such as chromous chloride or titanous chloride, and the second requires a preliminary reduction of uranium to the (IV) or (III) state, followed by titration back to the (VI) state with a standard oxidant. Both types of redox titrations are discussed. 4 figs

The Amster concept: a configuration generating its own uranium with a mixed thorium and uranium support

International Nuclear Information System (INIS)

Vergnes, J.; Garzenne, C.; Lecarpentier, D.; Mouney, H.; Delpech, M.

2001-01-01

AMSTER is a continuously reloaded, graphite-moderated molten salt critical reactor, using a 238 U or 232 Th fuel support, slightly enriched with 235 U if necessary. Using this concept, one can define a large number of configurations according to the products loaded and recycled. The choice of thorium fuel support leads to two configurations requiring no additional 235 U as fissile material: a configuration with one moderating zone, incinerating Transuranium elements (TRU); a configuration with 2 moderating zones self-consuming TRU and regenerating the fissile uranium ( 233 U). In this configuration, it is even possible to burn 238 U (from depleted uranium) by adding it to the thorium support. These configurations use a minimum amount of fuel (100 kg of 232 Th or 100 kg of a 232 Th- 238 U mix per TWh) and produce very little TRU (a few tens of grams per TWh). (author)

Validation of the Monte Carlo criticality program KENO IV and the Hansen-Roach sixteen-energy-group-cross sections for high-assay uranium systems

International Nuclear Information System (INIS)

Handley, G.R.; Masters, L.C.; Stachowiak, R.V.

1981-01-01

Validation of the Monte Carlo criticality code, KENO IV, and the Hansen-Roach sixteen-energy-group cross sections was accomplished by calculating the effective neutron multiplication constant, k/sub eff/, of 29 experimentally critical assemblies which had uranium enrichments of 92.6% or higher in the uranium-235 isotope. The experiments were chosen so that a large variety of geometries and of neutron energy spectra were covered. Problems, calculating the k/sub eff/ of systems with high-uranium-concentration uranyl nitrate solution that were minimally reflected or unreflected, resulted in the separate examination of five cases

Potentiometric determination of hexavalent uranium in uranium silicide samples

International Nuclear Information System (INIS)

Arlegui, Oscar

1999-01-01

The Chilean Nuclear Energy Commission's Department of Nuclear Materials has among its projects the production of fuels elements for nuclear reactors, and, therefore, the Chemical Analysis Laboratory must have a rapid and reliable method for uranium analysis, to control the uranium concentration during each stage of the production process. For this reason the Chilean Nuclear Energy Commission's Chemical Analysis Laboratory has validated a potentiometric method, which is a modification of the Davies and Gray method proposed by A.R. Eberle. This method uses the Potentiometric Titration Technique and is based on the direct and rapid reduction of uranium (VI) to Uranium (IV), in a concentrated phosphoric acid medium, with excess iron (II) used as a reducing agent. In this medium the excess iron (II) selectively oxidizes to iron (III) with nitric acid, using molybdenum (IV) as a catalyzer, the nitrous acid that is produced is eliminated by adding amidosulfuric acid. The solution is diluted with 1M sulfuric acid and the uranium (IV) obtained is titrated potentiometrically with potassium dichromate in the presence of vanadilic sulfate to obtain a better defined final titration point. The samples were softened with hydrochloric acid and nitric acid and later 50 ml were estimated in a 20% sulfuric acid medium. The analytical method was validated by comparing it with Certified Reference Material (C.R.M.) from the New Brunswick Laboratory (NBL), Metallic Uranium, CRM 112-A. The F Test and the T Test show that the value calculated is less than the tabulated value so the result is traceable to the reference material. The quantification limit, sensitivity, precision and accuracy were quantified for the method

About the structure and stability of complex carbonates of thorium (IV), cerium (IV), zirconium (IV), hafnium (IV)

International Nuclear Information System (INIS)

Dervin, Jacqueline

1972-01-01

This research thesis addressed the study of complex carbonates of cations of metals belonging to the IV A column, i.e. thorium (IV), zirconium (IV), hafnium (IV), and also cerium (IV) and uranium (VI), and more particularly focused on ionic compounds formed in solution, and also on the influence of concentration and nature of cations on stability and nature of the formed solid. The author first presents methods used in this study, discusses their precision and scope of validity. She reports the study of the formation of different complex ions which have been highlighted in solution, and the determination of their formation constants. She reports the preparation and study of the stability domain of solid complexes. The next part reports the use of thermogravimetric analysis, IR spectrometry, and crystallography for the structural study of these compounds

Synthesis, structure, spectroscopy and redox energetics of a series of uranium(4) mixed-ligand metallocene complexes

Energy Technology Data Exchange (ETDEWEB)

Thomson, R.K.; Scott, B.L.; Morris, D.E.; Kiplinger, J.L. [Los Alamos National Laboratory, Los Alamos, NM (United States)

2010-06-15

A series of uranium(IV) mixed-ligand amide-halide/pseudo-halide complexes (C{sub 5}Me{sub 5}){sub 2}U[N(SiMe{sub 3}){sub 2}](X) (X = F (1), Cl (2), Br (3), I (4), N{sub 3} (5), NCO (6)), (C{sub 5}Me{sub 5}){sub 2}U(NPh{sub 2})(X) (X = Cl (7), N{sub 3} (8)), and (C{sub 5}Me{sub 5}){sub 2}U[N(Ph)(SiMe{sub 3})](X) (X Cl (9), N{sub 3} (10)) have been prepared by one electron oxidation of the corresponding uranium(III) amide precursors using either copper halides, silver iso-cyanate, or triphenylphosphine gold(I)azide. Agostic U---H-C interactions and {eta}{sub 3}-(N,C,C') coordination are observed for these complexes in both the solid-state and solution. There is a linear correlation between the chemical shift values of the C{sub 5}Me{sub 5} ligand protons in the {sup 1}H NMR spectra and the U(IV)/U(III) reduction potentials of the (C{sub 5}Me{sub 5}){sub 2}U[N(SiMe{sub 3}){sub 2}](X) complexes, suggesting that there is a common origin, that is overall {sigma}-/{pi}-donation from the ancillary (X) ligand to the metal, contributing to both observables. Optical spectroscopy of the series of complexes 1-6 is dominated by the (C{sub 5}Me{sub 5}){sub 2}U[N(SiMe{sub 3}){sub 2}] core, with small variations derived from the identity of the halide/pseudo-halide. The considerable {pi}-donating ability of the fluoride ligand is reflected in both the electrochemistry and UV-visible-NIR spectroscopic behavior of the fluoride complex (C{sub 5}Me{sub 5}){sub 2}U[N(SiMe{sub 3}){sub 2}](F) (1). The syntheses of the new trivalent uranium amide complex, (C{sub 5}Me{sub 5}){sub 2}U[N(Ph)(SiMe{sub 3})](THF), and the two new weakly-coordinating electrolytes, [Pr{sub 4}N][B{l_brace}3,5-(CF{sub 3}){sub 2}C{sub 6}H{sub 3{r_brace}4}] and [Pr{sub 4}N][B(C{sub 6}F{sub 5}){sub 4}], are also reported. (authors)

Reduction of uranium(IV) and its mixtures with an olefin or an alkyne in tetrahydrofuran solutions by solvated electrons

International Nuclear Information System (INIS)

Koulkes-Pujo, A.M.; Le Marechal, J.F.; Le Motais, B.; Folcher, G.

1985-01-01

The reduction of UCl 4 and its mixtures with different olefins (stilbene, St, diphenylethylene, DPE, acenaphtylene, Ac or with diphenylacetylene (DPA) was studied by pulse radiolysis of tetrahydrofuran (THF) solutions. U(III) was formed by U(IV) reaction either with the solvated electrons created by THF radiolysis or with the transitory anions St - and DPA - . In the latter case, the reaction proceeds via a first step leading to [St-U(IV)] - or [DPA-U(IV)] - . In the case of DPE - the first species, [DPE-U(IV)] - , does not lead to U(III) but is destroyed by THF(H) + giving DPE(H). and U(IV). Ac - does not react with U(IV). A mechanistic scheme of this electron attachment is discussed as well as its implication in catalytic hydrogenation of olefins in LiAlH 4 -UCl 4 solutions. It is concluded that the catalytic effect observed is rather the result of a hydride transfer from a uranium transient compound to the alkenes. 22 references, 8 figures, 1 table

Energies and electric dipole transitions for low-lying levels of protactinium IV and uranium V

Energy Technology Data Exchange (ETDEWEB)

Uerer, Gueldem; Oezdemir, Leyla [Sakarya Univ. (Turkey). Physics Dept.

2012-01-15

We have reported a relativistic multiconfiguration Dirac-Fock (MCDF) study on low-lying level structures of protactinium IV (Z = 91) and uranium V (Z = 92) ions. Excitation energies and electric dipole (E1) transition parameters (wavelengths, oscillator strengths, and transition rates) for these low-lying levels have been given. We have also investigated the influence of the transverse Breit and quantum electrodynamic (QED) contributions besides correlation effects on the level structure. A comparison has been made with a few available data for these ions in the literature. (orig.)

URANIUM LEACHING AND RECOVERY PROCESS

Science.gov (United States)

McClaine, L.A.

1959-08-18

A process is described for recovering uranium from carbonate leach solutions by precipitating uranium as a mixed oxidation state compound. Uranium is recovered by adding a quadrivalent uranium carbon;te solution to the carbonate solution, adjusting the pH to 13 or greater, and precipitating the uranium as a filterable mixed oxidation state compound. In the event vanadium occurs with the uranium, the vanadium is unaffected by the uranium precipitation step and remains in the carbonate solution. The uranium-free solution is electrolyzed in the cathode compartment of a mercury cathode diaphragm cell to reduce and precipitate the vanadium.

Process for recovery of plutonium from fabrication residues of mixed fuels consisting of uranium oxide and plutonium oxide

International Nuclear Information System (INIS)

Heremanns, R.H.; Vandersteene, J.J.

1983-01-01

The invention concerns a process for recovery of plutonium from fabrication residues of mixed fuels consisting of uranium oxide and plutonium oxide in the form of PuO 2 . Mixed fuels consisting of uranium oxide and plutonium oxide are being used more and more. The plants which prepare these mixed fuels have around 5% of the total mass of fuels as fabrication residue, either as waste or scrap. In view of the high cost of plutonium, it has been attempted to recover this plutonium from the fabrication residues by a process having a purchase price lower than the price of plutonium. The problem is essentially to separate the plutonium, the uranium and the impurities. The residues are fluorinated, the UF 6 and PuF 6 obtained are separated by selective absorption of the PuF 6 on NaF at a temperature of at least 400 0 C, the complex obtained by this absorption is dissolved in nitric acid solution, the plutonium is precipitated in the form of plutonium oxalate by adding oxalic acid, and the precipitated plutonium oxalate is calcined

Solvent extraction of uranium(VI) and thorium(IV) from nitrate media by carboxylic acid amides

International Nuclear Information System (INIS)

Preston, J.S.; Preez, A.C. du

1995-01-01

A series of nineteen N-alkyl carboxylic acid amides (R.CO.NHR') has been prepared, in which the alkyl groups R and R' have been varied in order to introduce different degrees of steric complexity into the compounds. A smaller number of N,N-dialkyl amides (R.CO.NR 2 ') and non-substituted amides (R.CO.NH 2 ) has also been prepared for comparison purposes. These amides were characterized by measurement of their boiling points, melting points, refractive indices and densities. The solvent extraction of uranium(VI) and thorium(IV) from sodium nitrate media by solutions of the amides in toluene was studied. Increasing steric bulk of the alkyl groups R and R' was found to cause a marked decrease in the extraction of thorium, with a much smaller effect on the extraction of uranium, thus considerably enhancing the separation between these metals. Vapour pressure osmometry studies indicate that the N-alkyl amides are self-associated in toluene solution, with aggregation numbers up to about 2.5 for 0.6 M solutions at 35 degree C. In contrast, the N,N-dialkyl amides behave as monomers under these conditions. The distribution ratios for the extraction of uranium and thorium show second- and third-order dependences, respectively, on the extractant concentration for both the N-alkyl and N,N-dialkyl amides. 15 refs., 8 figs., 8 tabs

Processing Pa-Lua Uranium ore by Mixing and Curing with Sulfuric Acid on a Scale of 500 kg/Batch to Recover Yellowcake

International Nuclear Information System (INIS)

Le Quang Thai; Cao Hung Thai; Le Thi Kim Dung; Phung Vu Phong; Tran Van Son

2007-01-01

Uranium ore in Pa-Lua area is sandstone with different levels of weathering. This kind of ore contains calcium and clay that may cause clogs during heap leaching. In this study, a technique of mixing and curing with strong acids is used and followed by washing to recover uranium. This study also focuses on study of ore processing issues such as crushing, regenerating particles in fine ores, mixing, curing and washing. The leach solution is treated by ion-exchange and precipitation of products by NH 4 OH. The experiment results show that regenerating a portion of fine ores, mixing and curing help washing residues in the column more effectively. Flow rate of the input solution can be controllable and stable. Columns do not clog even when washing takes place in the ore column of 5 meters high. Efficiency of uranium recovery can reach to 85-90%. Products of technical uranium are obtained with high quality. (author)

Determination of plutonium and uranium in mixed nuclear fuel by means of potentiostatic and amperostatic coulometry

International Nuclear Information System (INIS)

Kuperman, A.Ya.; Moiseev, I.V.; Galkina, V.N.; Yakushina, G.S.; Nikitskaya, V.N.

1977-01-01

Product solution occurs in HClO 4 + HNO 3 mixing. In prepared plutonium (6) and uranium (6) perchloric acid solution Cl and Cr (6), Mn (7,6,3) foreign oxidizers are selectively reduced with formic and malonic acids. Potentiostatic variant of method is based on successive reduction of Pu(6) to Pu(3) and U(6) to U(4) in 4.5M HCl, containing 5x10 -4 M bismuth (3). In using amperostatic variant of method plutonium and uranium are determined separately. In sulfur-phosphoric acid media plutonium (6) is titrated to Pu(4) with continuously generated iron (2) ions. Uranium (6) in phosphoric acid media is initially reduced to U(4) with Fe(2), and then after Fe(2) excess reduction with nitric acid it is titrated to uranium (6) with continuously electrogenerated manganese (3) ions or vanadium (5). To obtain equivalent point in plutonium (6) and uranium (4) titration amperometric method is used. Coefficient of variation is 0.2-0.3 % rel

Recovery of uranium from uranium bearing black shale

International Nuclear Information System (INIS)

Das, Amrita; Yadav, Manoj; Singh, Ajay K.

2016-01-01

Black shale is the unconventional resource of uranium. Recovery of uranium from black shale has been carried out by the following steps: i) size reduction, ii) leaching of uranium in the aqueous medium, iii) fluoride ion removal, iv) solvent extraction of uranium from the aqueous leach solution, v) scrubbing of the loaded solvent after extraction to remove impurities as much as possible and vi) stripping of uranium from the loaded organic into the aqueous phase. Leaching of black shale has been carried out in hydrochloric acid. Free acidity of the leach solution has been determined by potentiometric titration method. Removal of fluoride ions has been done using sodium chloride. Solvent extraction has been carried out by both tributyl phosphate and alamine-336 as extractants. Scrubbing has been tried with oxalic acid and sulphuric acid. Stripping with sodium carbonate solution has been carried out. Overall recovery of uranium is 95%. (author)

Analysis of refabricated fuel: determination of carbon in uranium plutonium mixed carbide

International Nuclear Information System (INIS)

Huwyler, S.

1977-09-01

In developing uranium plutonium mixed carbide which represents an advanced fuel for breeder reactors carbon analysis is an important means of determining the stoichiometry. Methods of carbon determination are briefly reviewed. The carbon determination using a LECO WR-12 Carbon Determinator is treated in detail and experience of three years operation communicated. Problems arising from operating the LECO-apparatus in a glove box are discussed. It is pointed out that carbon determination with the LECO-apparatus is a very fast method with good precision and well suited for the routine analysis of mixed carbide fuel. The accuracy of the method is checked by means of a standard. (Auth.)

Spectrophotometric Microdetermination of Thorium(IV and Uranium(VI with Chrome Azurol-S in Presence of Cationic Surfactant

Directory of Open Access Journals (Sweden)

A. B. Upase

2011-01-01

Full Text Available Cationic surfactant, cetyldimethylethylammonium bromide (CDMEAB, sensitize the color reactions of Th(IV and U(VI with chrome azurol-S(CRAS. Formation of water soluble deeply colored ternary complexes of metal ions show large bathochromic shift. Same stoichiometric composition of ternary complexes with 1:2:4 molar ratio (M-CRAS-CDMEAB have been observed for both the metal ions and are responsible for enhancement in molar absorptivities and sensitivities at shifted wavelength. The ternary complexes of thorium(IV and uranium(VI exhibit absorption maxima at 640 and 620 nm with molar absorptivities 85500 and 69600 L.mol-1.cm-2 respectively. Beer’s law were obeyed in concentration range 0.12-0.185 ppm for Th(IV and 0.13-0.162 ppm for U(VI in presence of CDMEAB. Conditional formation constants and various analytical parameters have been evaluated and compared the results of binary and ternary complexes. Enhancement in the molar absorptivities in presence of CDMEAB clearly indicated the usefulness of these colored reactions for microdetermination.

Uranium redox transition pathways in acetate-amended sediments

Science.gov (United States)

Bargar, John R.; Williams, Kenneth H.; Campbell, Kate M.; Long, Philip E.; Stubbs, Joanne E.; Suvorova, Elenal I.; Lezama-Pacheco, Juan S.; Alessi, Daniel S.; Stylo, Malgorzata; Webb, Samuel M.; Davis, James A.; Giammar, Daniel E.; Blue, Lisa Y.; Bernier-Latmani, Rizlan

2013-01-01

Redox transitions of uranium [from U(VI) to U(IV)] in low-temperature sediments govern the mobility of uranium in the environment and the accumulation of uranium in ore bodies, and inform our understanding of Earth’s geochemical history. The molecular-scale mechanistic pathways of these transitions determine the U(IV) products formed, thus influencing uranium isotope fractionation, reoxidation, and transport in sediments. Studies that improve our understanding of these pathways have the potential to substantially advance process understanding across a number of earth sciences disciplines. Detailed mechanistic information regarding uranium redox transitions in field sediments is largely nonexistent, owing to the difficulty of directly observing molecular-scale processes in the subsurface and the compositional/physical complexity of subsurface systems. Here, we present results from an in situ study of uranium redox transitions occurring in aquifer sediments under sulfate-reducing conditions. Based on molecular-scale spectroscopic, pore-scale geochemical, and macroscale aqueous evidence, we propose a biotic–abiotic transition pathway in which biomass-hosted mackinawite (FeS) is an electron source to reduce U(VI) to U(IV), which subsequently reacts with biomass to produce monomeric U(IV) species. A species resembling nanoscale uraninite is also present, implying the operation of at least two redox transition pathways. The presence of multiple pathways in low-temperature sediments unifies apparently contrasting prior observations and helps to explain sustained uranium reduction under disparate biogeochemical conditions. These findings have direct implications for our understanding of uranium bioremediation, ore formation, and global geochemical processes.

Rapid non-destructive quantitative estimation of urania/ thoria in mixed thorium uranium di-oxide pellets by high-resolution gamma-ray spectrometry

Energy Technology Data Exchange (ETDEWEB)

Shriwastwa, B.B.; Kumar, Anil; Raghunath, B.; Nair, M.R.; Abani, M.C.; Ramachandran, R.; Majumdar, S.; Ghosh, J.K

2001-06-01

A non-destructive technique using high-resolution gamma-ray spectrometry has been standardised for quantitative estimation of uranium/thorium in mixed (ThO{sub 2}-UO{sub 2}) fuel pellets of varying composition. Four gamma energies were selected; two each from the uranium and thorium series and the time of counting has been optimised. This technique can be used for rapid estimation of U/Th percentage in a large number of mixed fuel pellets from a production campaign.

Rapid non-destructive quantitative estimation of urania/ thoria in mixed thorium uranium di-oxide pellets by high-resolution gamma-ray spectrometry

International Nuclear Information System (INIS)

Shriwastwa, B.B.; Kumar, Anil; Raghunath, B.; Nair, M.R.; Abani, M.C.; Ramachandran, R.; Majumdar, S.; Ghosh, J.K.

2001-01-01

A non-destructive technique using high-resolution gamma-ray spectrometry has been standardised for quantitative estimation of uranium/thorium in mixed (ThO 2 -UO 2 ) fuel pellets of varying composition. Four gamma energies were selected; two each from the uranium and thorium series and the time of counting has been optimised. This technique can be used for rapid estimation of U/Th percentage in a large number of mixed fuel pellets from a production campaign

Chloride pyrometallurgy of uranium ore. 2. Selective extraction of uranium using the mixed gas of chlorine and oxygen in the presence of activated carbon

International Nuclear Information System (INIS)

Taki, Tomihiro; Komoto, Shigetoshi; Otomura, Keiichiro; Takenaka, Toshihide; Sato, Nobuaki; Fujino, Takeo.

1996-01-01

Selective extraction of uranium from a phosphate ore was studied by using the mixed gas of Cl 2 and O 2 . On heating the ore and carbon mixture in Cl 2 , the volatilized chloride of uranium is accompanied by iron, aluminum, phosphorus and silicon chlorides. The addition of O 2 gas effectively lowered the volatilization ratios of aluminum, phosphorus and silicon. The ratio decreased with increasing oxygen flow rate up to 50 ml/min at 1,223 K (Cl 2 : 100 ml/min, O 2 +N 2 : 400 ml/min). The volatilization ratio of uranium was almost unchanged at 90% up to 50 ml/min O 2 (carbon amount: 15 wt%). The effect of the other parameters, i.e. Cl 2 flow rate, carbon amount, reaction temperature and time was examined. (author)

Synthesis and characterization of chiral thorium(IV) and uranium(IV) benzamidinate complexes

Energy Technology Data Exchange (ETDEWEB)

Schoene, Sebastian; Maerz, Juliane; Kaden, Peter; Patzschke, Michael; Ikeda-Ohno, Atsushi [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Chemistry of the F-Elements

2017-06-01

Two chiral benzamidinate complexes of tetravalent actinides (Th(IV) and U(IV)) were synthesized using a salt metathesis reaction of the corresponding actinide(IV) tetrachlorides and the potassium salt of the chiral benzamidine (S,S)-N,N-Bis-(1-phenylethyl)-benzamidine ((S)-HPEBA). The structure of the complexes was determined with single crystal X-ray diffraction. These are the first examples of chiral amidinate complexes of actinides.

Exploration and uranium mining in Niger

International Nuclear Information System (INIS)

Moussa, M.

2014-01-01

features are important in trapping the mineralisation which is often of roll front type, either reduced consisting in pitchblende and coffinite (Akouta, Arlit, Afasto, Madaouela) or oxidized (Imouraren). The main exploration companies of Uranium in the basin of Tim Mersoï (Northern Iullemenden) are: • AREVA-Niger for the uranium-bearing prospecting permits of Imouraren, Afouday, Agebout; • Cominak for the uranium-bearing prospecting permit Western Afasto; • NorthWestern Mineral Ventures Inc for the uranium-bearing prospecting permits Irhazer and Ingal; • North Atlantic Resources Ltd. for the uranium-bearing prospecting permit Abélajouad; • CNUC for the uranium-bearing permit of Tiguida • Goviex for uranium permit of Madaouéla; • International Uranium Ltd for the uranium-bearing prospecting permits of Agelal I, II, III, IV and Aserka I, II, III, IV; • Total Uranium Corporation for the licences of Chock Negouran I, II, III and IV; • Trend Field Holding SA for the uranium-bearing prospecting permits Tagaza II and IV. (author)

Precise coulometric titration of uranium in a high-purity uranium metal and in uranium compounds

International Nuclear Information System (INIS)

Tanaka, Tatsuhiko; Yoshimori, Takayoshi

1975-01-01

Uranium in uranyl nitrate, uranium trioxide and a high-purity uranium metal was assayed by the coulometric titration with biamperometric end-point detection. Uranium (VI) was reduced to uranium (IV) by solid bismuth amalgam in 5M sulfuric acid solution. The reduced uranium was reoxidized to uranium (VI) with a large excess of ferric ion at a room temperature, and the ferrous ion produced was titrated with the electrogenerated manganese(III) fluoride. In the analyses of uranium nitrate and uranium trioxide, the results were precise enough when the error from uncertainty in water content in the samples was considered. The standard sample of pure uranium metal (JAERI-U4) was assayed by the proposed method. The sample was cut into small chips of about 0.2g. Oxides on the metal surface were removed by the procedure shown by National Bureau of Standards just before weighing. The mean assay value of eleven determinations corrected for 3ppm of iron was (99.998+-0.012) % (the 95% confidence interval for the mean), with a standard deviation of 0.018%. The proposed coulometric method is simple and permits accurate and precise determination of uranium which is matrix constituent in a sample. (auth.)

Electrochemical investigation of uranium β-diketonates for all-uranium redox flow battery

International Nuclear Information System (INIS)

Yamamura, Tomoo; Shiokawa, Yoshinobu; Yamana, Hajimu; Moriyama, Hirotake

2002-01-01

The redox flow battery using uranium as the negative and the positive active materials in polar aprotic solvents was proposed. In order to establish the guiding principle for the uranium compounds as the active materials, the investigation of uranium β-diketonate complexes was conducted on (i) the solubility of active materials, (ii) the electrode reaction of U(VI) and U(IV) β-diketonate complexes and (iii) the estimation of the open circuit voltage of the battery. The solubilities of higher than 0.8 mol dm -3 of U(VI) complexes and higher than 0.4 mol dm -3 of a U(IV) complex were obtained in the solvents. The electrode reactions of U(pta) 4 , UO 2 (dpm) 2 , UO 2 (fod) 2 and UO 2 (pta) 2 were first studied and the redox potentials of uranium β-diketonates were thermodynamically discussed. The open circuit voltage is estimated more than 1 V by using Hacac or Hdpm. The larger open circuit voltage is expected when a ligand with the larger basicity is used

Study on the uranium-cerium extraction and his application to the treatment of irradiated uranium

International Nuclear Information System (INIS)

Lobao, Afonso dos Santos Tome

1979-01-01

It was made a study on the behavior of uranium and cerium(IV) extraction, using the latter element as a plutonium simulator in a flowsheet of the treatment of irradiated uranium. Cerium(IV) was used under the same conditions as a plutonium in the Purex process because the admitted similar properties. An experimental work was initiated to determine the equilibrium curves of uranium, under the following conditions: concentration of 1 to 20 g U/1 and acidity varying from 1 to 5M in HNO 3 . Other parameters studied were the volumetric ratio of the phases and the influence of the concentration of TBP (tri-n-butyl phosphate). To guarantee the cerium(IV) extraction, the diluent (varsol) was previously treated with 10% potassium dichromate in perchloric acid, potassium permanganate in 1M sulphuric acid and concentrated sulphuric acid at 70 deg to eliminate reducing compounds. The results obtained for cerium extraction, allowed a better understanding of its behavior in solution. The results permitted to conclude that the decontamination for cerium are very high in the first Purex extraction cycle. The easy as cerium(IV) is reduced to the trivalent state contributes a great deal to its decontamination. (author)

The prospect of uranium nitride (UN) and mixed nitride fuel (UN-PuN) for pressurized water reactor

International Nuclear Information System (INIS)

Syarifah, Ratna Dewi; Suud, Zaki

2015-01-01

Design study of small Pressurized Water Reactors (PWRs) core loaded with uranium nitride fuel (UN) and mixed nitride fuel (UN-PuN), Pa-231 as burnable poison, and Americium has been performed. Pa-231 known as actinide material, have large capture cross section and can be converted into fissile material that can be utilized to reduce excess reactivity. Americium is one of minor actinides with long half life. The objective of adding americium is to decrease nuclear spent fuel in the world. The neutronic analysis results show that mixed nitride fuel have k-inf greater than uranium nitride fuel. It is caused by the addition of Pu-239 in mixed nitride fuel. In fuel fraction analysis, for uranium nitride fuel, the optimum volume fractions are 45% fuel fraction, 10% cladding and 45% moderator. In case of UN-PuN fuel, the optimum volume fractions are 30% fuel fraction, 10% cladding and 60% coolant/ moderator. The addition of Pa-231 as burnable poison for UN fuel, enrichment U-235 5%, with Pa-231 1.6% has k-inf more than one and excess reactivity of 14.45%. And for mixed nitride fuel, the lowest value of reactivity swing is when enrichment (U-235+Pu) 8% with Pa-231 0.4%, the excess reactivity value 13,76%. The fuel pin analyze for the addition of Americium, the excess reactivity value is lower than before, because Americium absorb the neutron. For UN fuel, enrichment U-235 8%, Pa-231 1.6% and Am 0.5%, the excess reactivity is 4.86%. And for mixed nitride fuel, when enrichment (U-235+Pu) 13%, Pa-231 0.4% and Am 0.1%, the excess reactivity is 11.94%. For core configuration, it is better to use heterogeneous than homogeneous core configuration, because the radial power distribution is better

The prospect of uranium nitride (UN) and mixed nitride fuel (UN-PuN) for pressurized water reactor

Science.gov (United States)

Syarifah, Ratna Dewi; Suud, Zaki

2015-09-01

Design study of small Pressurized Water Reactors (PWRs) core loaded with uranium nitride fuel (UN) and mixed nitride fuel (UN-PuN), Pa-231 as burnable poison, and Americium has been performed. Pa-231 known as actinide material, have large capture cross section and can be converted into fissile material that can be utilized to reduce excess reactivity. Americium is one of minor actinides with long half life. The objective of adding americium is to decrease nuclear spent fuel in the world. The neutronic analysis results show that mixed nitride fuel have k-inf greater than uranium nitride fuel. It is caused by the addition of Pu-239 in mixed nitride fuel. In fuel fraction analysis, for uranium nitride fuel, the optimum volume fractions are 45% fuel fraction, 10% cladding and 45% moderator. In case of UN-PuN fuel, the optimum volume fractions are 30% fuel fraction, 10% cladding and 60% coolant/ moderator. The addition of Pa-231 as burnable poison for UN fuel, enrichment U-235 5%, with Pa-231 1.6% has k-inf more than one and excess reactivity of 14.45%. And for mixed nitride fuel, the lowest value of reactivity swing is when enrichment (U-235+Pu) 8% with Pa-231 0.4%, the excess reactivity value 13,76%. The fuel pin analyze for the addition of Americium, the excess reactivity value is lower than before, because Americium absorb the neutron. For UN fuel, enrichment U-235 8%, Pa-231 1.6% and Am 0.5%, the excess reactivity is 4.86%. And for mixed nitride fuel, when enrichment (U-235+Pu) 13%, Pa-231 0.4% and Am 0.1%, the excess reactivity is 11.94%. For core configuration, it is better to use heterogeneous than homogeneous core configuration, because the radial power distribution is better.

Separation of uranium isotopes by accelerated isotope exchange reactions

International Nuclear Information System (INIS)

Seko, M.; Miyake, T.; Inada, K.; Ochi, K.; Sakamoto, T.

1977-01-01

A novel catalyst for isotope exchange reaction between uranium(IV) and uranium(VI) compounds enables acceleration of the reaction rate as much as 3000 times to make industrial separation of uranium isotopes economically possible

Calibration of the Lawrence Livermore National Laboratory Passive-Active Neutron Drum Shuffler for Measurement of Highly Enriched Uranium in Mixed Oxide

International Nuclear Information System (INIS)

Mount, M.; O'Connell, W.; Cochran, C.; Rinard, P.; Dearborn, D.; Endres, E.

2002-01-01

As a follow-on to the Lawrence Livermore National Laboratory (LLNL) effort to calibrate the LLNL passive-active neutron drum (PAN) shuffler for measurement of highly enriched uranium (HEU) oxide, a method has been developed to extend the use of the PAN shuffler to the measurement of HEU in mixed uranium-plutonium (U-Pu) oxide. This method uses the current LLNL HEU oxide calibration algorithms, appropriately corrected for the mixed U-Pu oxide assay time, and recently developed PuO 2 calibration algorithms to yield the mass of 235 U present via differences between the expected count rate for the PuO 2 and the measured count rate of the mixed U-Pu oxide. This paper describes the LLNL effort to use PAN shuffler measurements of units of certified reference material (CRM) 149 (uranium (93% Enriched) Oxide - U 3 O 8 Standard for Neutron Counting Measurements) and CRM 146 (uranium Isotopic Standard for Gamma Spectrometry Measurements) and a selected set of LLNL PuO 2 -bearing containers in consort with Monte Carlo simulations of the PAN shuffler response to each to (1) establish and validate a correction to the HEU calibration algorithm for the mixed U-Pu oxide assay time, (2) develop a PuO 2 calibration algorithm that includes the effect of PuO 2 density (2.4 g/cm 3 to 4.8 g/cm 3 ) and container size (8.57 cm to 9.88 cm inside diameter and 9.60 cm to 13.29 cm inside height) on the PAN shuffler response, and (3) develop and validate the method for establishing the mass of 235 U present in an unknown of mixed U-Pu oxide.

Advances on reverse strike co-precipitation method of uranium-plutonium mixed solutions

International Nuclear Information System (INIS)

Menghini, Jorge E.; Marchi, Daniel E.; Orosco, Edgardo H.; Greco, Luis

2000-01-01

The reverse strike coprecipitation of uranium-plutonium mixed solutions, is an alternative way to obtain MOX fuel pellets. Previous tests, carried out in the Alpha Laboratory, included a stabilization step for transforming 100 % of plutonium into Pu +4 . Therefore, the plutonium precipitated as Pu(OH) 4 . In this second step, the stabilization process was suppressed. In this way, besides Pu(OH) 4 , a part of the precipitated is composed of a mixed salt: AD(U,Pu). Then, a homogeneous solid solution is formed in the early steps of the process. The powders showed higher tap density, better performance during the pressing and lower sinterability than the powders obtained in previous tests. The advantageous and disadvantageous effects of the stabilization step are analyzed in this paper. (author)

Sorption behaviour of uranium and thorium on hydrous tin oxide from aqueous and mixed-solvent HNO3 media

International Nuclear Information System (INIS)

Misak, N.Z.; Salama, H.N.; El-Naggar, I.M.

1983-01-01

In aqueous nitric acid, uranyl and thorium ions seem to be sorbed on hydrous tin oxide mainly by a cation exchange mechanism. In 10 - 3 M aqueous solutions, the hydrous oxide prefers thorium to uranium at the relative low pH values, while the reverse is true at the higher pH values. The exchange of uranium is particle diffusion controlled while that of thorium is chemically controlled, and the isotherms point to the presence of different-energy sites in the hydrous oxide. Except for the solutions containing 80% of methanol, ethanol, or acetone, cation exchange is probably still the main mechanism of sorption of uranium. Anionic sorption of thorium seems to occur in all the mixed-solvent solutions and is perhaps the main mechanism in 80% ethanol. The equilibrium distribution coefficient K sub (d) increases almost in all cases with organic solvent content, probably due to dehydration of sorbed ions and to increasing superposition on anionic sorption. Unlike the aqueous medium, large U/Th separation factors are achieved in many of the mixed-solvent solutions and separation schemes are suggested. (Authors)

Determination of uranium (IV) by flow voltammetry

International Nuclear Information System (INIS)

Ding Anqing

1987-01-01

According to the quantitative reaction of U(IV) and Fe(III) in H 2 SO 4 as well as the relation between current and concentration of substance detected, U(IV) has been determined indirectly by measurement of the electrolysis current of residual Fe(III). The columniform electrode used is made of glass carbon particles. At the range of U(IV) from a few micrograms to 40 μg, the linear relation is excellent. The relative standard deviation is within ±4%. The interference of Fe(II), Ti(IV) and U(VI) is negligible but of Ti(III) is serious. This method has been successfully applied in the determination of actual samples (both out line and on line). Main advantages of this procedure are rapid, simple, small amount of sample (only at microgram level) and easy to realize automation, able to use for on line or process analysis

Gen IV. Technical and economical aspects

International Nuclear Information System (INIS)

Kaluzny, Y.; Legee, F.

2010-01-01

In this presentation author deals with development of nuclear reactor type of Generation IV. He concluded that: - Nuclear energy is competitive with regards to the other generation sources; Its competitiveness also increases with CO 2 cost. Considering the nuclear cost breakdown of LWR reactors, it turns out that the uranium is currently not in the range of a threshold for FBR deployment; - The global balance of uranium supply and demand and also innovation required to fulfil GEN IV objectives would probably imply the emergence of fast reactor competitiveness after the turn of the mid-century; - We shall need fast reactors in the coming decade.

Oxidation of naturally reduced uranium in aquifer sediments by dissolved oxygen and its potential significance to uranium plume persistence

Science.gov (United States)

Davis, J. A.; Smith, R. L.; Bohlke, J. K.; Jemison, N.; Xiang, H.; Repert, D. A.; Yuan, X.; Williams, K. H.

2015-12-01

The occurrence of naturally reduced zones is common in alluvial aquifers in the western U.S.A. due to the burial of woody debris in flood plains. Such reduced zones are usually heterogeneously dispersed in these aquifers and characterized by high concentrations of organic carbon, reduced mineral phases, and reduced forms of metals, including uranium(IV). The persistence of high concentrations of dissolved uranium(VI) at uranium-contaminated aquifers on the Colorado Plateau has been attributed to slow oxidation of insoluble uranium(IV) mineral phases found in association with these reducing zones, although there is little understanding of the relative importance of various potential oxidants. Four field experiments were conducted within an alluvial aquifer adjacent to the Colorado River near Rifle, CO, wherein groundwater associated with the naturally reduced zones was pumped into a gas-impermeable tank, mixed with a conservative tracer (Br-), bubbled with a gas phase composed of 97% O2 and 3% CO2, and then returned to the subsurface in the same well from which it was withdrawn. Within minutes of re-injection of the oxygenated groundwater, dissolved uranium(VI) concentrations increased from less than 1 μM to greater than 2.5 μM, demonstrating that oxygen can be an important oxidant for uranium in such field systems if supplied to the naturally reduced zones. Dissolved Fe(II) concentrations decreased to the detection limit, but increases in sulfate could not be detected due to high background concentrations. Changes in nitrogen species concentrations were variable. The results contrast with other laboratory and field results in which oxygen was introduced to systems containing high concentrations of mackinawite (FeS), rather than the more crystalline iron sulfides found in aged, naturally reduced zones. The flux of oxygen to the naturally reduced zones in the alluvial aquifers occurs mainly through interactions between groundwater and gas phases at the water table

redox reactions of uranium in the presence of potassium 2-phospho-17-tungstate

International Nuclear Information System (INIS)

Maslov, L.P.; Rykov, A.G.; Sirotinkina, L.V.

1986-01-01

The redox reactions of uranium in the presence of potassium 2-phospho-17-tungstate (17W2P) - K 10 P 2 W 17 O 61 - were studied by the methods of spectrophotometry and potentiometry. It was established that in the presence of 17W2P the UO /SUP 2/2/ + ion is reduced by iron(II) to uranium(IV) as a result of the binding of U(IV) into a strong complex with composition (U(p 2 W 17 O 61 ) 2 ) 16- . The peculiarities of the coordination of uranium(IV) by voluminous 17W2P ligands are the cause of the different nature of its interaction with various types of oxidizing agents. It was established that under the action of oxidizing agents (K 2 Cr 2 O 7 , KMnO 4 ), the reduced form of which is a complex with 17W2P, there is a conversion of the complex of uranium(IV) to the corresponding complex of uranium(V), evidently with conservation of a structure analogous to that for uranium(IV). It was also shown that uranium(IV) in complex with 17W2P is practically not oxidized in the cold by persulfate ions which react according to a radical mechanism, whereas weaker oxidizing agents, for example, H 2 O 2 , oxidize it to the UO /SUP 2/2/ + ion. Hypotheses are advanced on the possible mechanisms of the occurrence of the corresponding reactions

Mild hydrothermal crystal growth of new uranium(IV) fluorides, Na3.13Mg1.43U6F30 and Na2.50Mn1.75U6F30: Structures, optical and magnetic properties

Science.gov (United States)

Yeon, Jeongho; Smith, Mark D.; Tapp, Joshua; Möller, Angela; zur Loye, Hans-Conrad

2016-04-01

Two new uranium(IV) fluorides, Na3.13Mg1.43U6F30 (1) and Na2.50Mn1.75U6F30 (2), were synthesized through an in situ mild hydrothermal route, and were structurally characterized by single crystal X-ray diffraction. The compounds exhibit complex crystal structures composed of corner- or edge-shared UF9 and MF6 (M=Mg, Mn) polyhedra, forming hexagonal channels in the three-dimensional framework, in which ordered or disordered divalent metal and sodium atoms reside. The large hexagonal voids contain the nearly regular M(II)F6 octahedra and sodium ions, whereas the small hexagonal cavities include M(II) and sodium ions on a mixed-occupied site. Magnetic susceptibility measurements yielded effective magnetic moments of 8.36 and 11.6 μB for 1 and 2, respectively, confirming the presence and oxidation states of U(IV) and Mn(II). The large negative Weiss constants indicate the spin gap between a triplet and a singlet state in the U(IV). Magnetization data as a function of applied fields revealed that 2 exhibits paramagnetic behavior due to the nonmagnetic singlet ground state of U(IV) at low temperature. UV-vis diffuse reflectance and X-ray photoelectron spectroscopy data were also analyzed.

High-temperature vaporization of thorium-uranium mixed monocarbide (Th1-y, Uy)C

International Nuclear Information System (INIS)

Koyama, Tadafumi; Yamawaki, Michio

1989-01-01

Vaporization thermodynamics of thorium-uranium mixed monocarbide phase (Th 1-y , U y )C was studied by mass spectrometric Knudsen effusion method for the compositions of (Th 0.9 , U 0.1 )C 0.855 , (Th 0.8 , U 0.2 )C 0.973 and (Th 0.6 , U 0.4 )C 0.973 . The partial vapor pressures of Th(g) and U(g) and activities of Th and U of these mixed monocarbides were determined at temperatures ranging from about 2000 to 2200 K. Further, the partial pressures of Th(g) and U(g) and activities of Th and U of the stoichiometric mixed monocarbides (Th 1-y , U y )C 1.00 were evaluated by compensating for the effect of carbon content. The Gibbs energies of formation of stoichiometric (Th 1-y , U y )C 1.00 were also evaluated. (orig.)

Inverse break-through investigation on uranium isotope separation in the system Fe(III) water-glycerine solution-U(IV) cathionic resin

International Nuclear Information System (INIS)

Murgulescu, Sanda; Calusaru, A.

1977-01-01

When a solution containing ferric ions passes on cationic resin in U(IV) form, the substitution of uranium by iron is preceded by oxydation of U(IV) to U(VI). During the contact of U(VI) in solution with U(IV) in resin, an exchange reaction occurs, in which 235 U is slightly concentrated in solution and 238 U in resin phase. Since increase of temperature accelerates the exchange reaction, the apparent thermodynamic values of the exchange reaction were calculated, by taking into account the variation of the apparent equilibrium constant as a function of the reciprocal value of the temperature. The corresponding thermodynamic values in both pure aqueous and water-glycerine solution are: ΔH 0 =6.45 cal.mol -1 and ΔS 0 =21.6x10 -3 cal. 0 K -1 . The use of glycerine containing solutions offers the important advantage to increase the stability versus hydrolysis of the ferric ions even at higher temperature

Recovery of uranium values

International Nuclear Information System (INIS)

Rowden, G.A.

1982-01-01

A process is provided for the recovery of uranium from an organic extractant phase containing an amine. The extractant phase is contacted in a number of mixing stages with an acidic aqueous stripping phase containing sulphate ions, and the phases are passed together through a series of mixing stages while maintaining a dispersion of droplets of one phase in the other. Uranium is precipitated from the final stage by raising the pH. An apparatus having several mixing chambers is described

U uranium. Suppl. Vol. D3

International Nuclear Information System (INIS)

Haug, H.O.

1982-01-01

This volume of the uranium series of the Gmelin handbook deals with the anion exchange of uranium. Compounds of the valence states of III, IV, V and VI of uranium in halide, nitrate, sulfate, phosphate, and carbonate media as well as in media containing organic complexing agents are treated. The literature cited covers the period from about 1947 to the end of 1980. (RB) [de

Valence-associated uranium isotope fractionation of uranium enriched phosphate in a shallow aquifer, Lee County, Florida

International Nuclear Information System (INIS)

Weinberg, J.M.; Levine, B.R.; Cowart, J.B.

1993-01-01

The source of anomalously high concentrations of uranium, characterized by U-234/U-238 activity ratios significantly less than unity, in shallow groundwaters of Lee County, Florida, was investigated. Uranium in cores samples was separated into U(IV) and U(VI) oxidation state fractions, and uranium analyses were conducted by alpha spectrometry. Uranium mobility was also studied in selected leaching experiments. Results indicate that mobilization of unusually soluble uranium, present in uranium enriched phosphate of the Pliocene age Tamiami Formation at determined concentrations of up to 729 ppm, is the source for high uranium concentrations in groundwater. In leaching experiments, approximately one-third of the uranium present in the uranium enriched phosphate was mobilized into the aqueous phase. Results of previous investigations suggest that U-234, produced in rock by U-238 decay, is selectively oxidized to U(VI). The uranium enriched phosphate studied in this investigation is characterized by selective reduction of U-234, with a pattern of increasing isotopic fractionation with core depth. As a consequence, U-234/U-238 activity ratios greater than 1.0 in the U(IV) fraction, and less than 1.0 in the U(VI) fraction have developed in the rock phase. In leaching experiments, the U(VI) fraction from the rock was preferentially mobilized into the aqueous phase, suggesting that U-234/U-238 activity ratios of leaching groundwaters are strongly influenced by the isotopic characteristics of the U(VI) fraction of rock. It is suggested that preferential leaching of U(VI), present in selectivity reduced uranium enriched phosphate, is the source for low activity ratio groundwaters in Lee County

Production of sized particles of uranium oxides and uranium oxyfluorides

International Nuclear Information System (INIS)

Knudsen, I.E.; Randall, C.C.

1976-01-01

A process is claimed for converting uranium hexafluoride (UF 6 ) to uranium dioxide (UO 2 ) of a relatively large particle size in a fluidized bed reactor by mixing uranium hexafluoride with a mixture of steam and hydrogen and by preliminary reacting in an ejector gaseous uranium hexafluoride with steam and hydrogen to form a mixture of uranium and oxide and uranium oxyfluoride seed particles of varying sizes, separating the larger particles from the smaller particles in a cyclone separator, recycling the smaller seed particles through the ejector to increase their size, and introducing the larger seed particles from the cyclone separator into a fluidized bed reactor where the seed particles serve as nuclei on which coarser particles of uranium dioxide are formed. 9 claims, 2 drawing figures

Uranium complex recycling method of purifying uranium liquors

International Nuclear Information System (INIS)

Elikan, L.; Lyon, W.L.; Sundar, P.S.

1976-01-01

Uranium is separated from contaminating cations in an aqueous liquor containing uranyl ions. The liquor is mixed with sufficient recycled uranium complex to raise the weight ratio of uranium to said cations preferably to at least about three. The liquor is then extracted with at least enough non-interfering, water-immiscible, organic solvent to theoretically extract about all of the uranium in the liquor. The organic solvent contains a reagent which reacts with the uranyl ions to form a complex soluble in the solvent. If the aqueous liquor is acidic, the organic solvent is then scrubbed with water. The organic solvent is stripped with a solution containing at least enough ammonium carbonate to precipitate the uranium complex. A portion of the uranium complex is recycled and the remainder can be collected and calcined to produce U 3 O 8 or UO 2

Methods for analysis of uranium-plutonium mixed fuel and transplutonium elements at RIAR (Preprint no. IT-25)

International Nuclear Information System (INIS)

Timofeev, G.A.

1991-02-01

Different methods for analysis of the uranium-plutonium mixed nuclear fuel and transplutonium elements are briefly discussed in this paper: coulometry, radiometric techniques, emission spectrography, mass-spectrometry, chromatography, spectrophotometry. The main analytical characteristics of the methods developed are given. (author). 30 refs., 2 tabs

Nuclear fuel technology - Determination of uranium in solutions, uranium hexafluoride and solids - Part 1: Iron(II) reduction/potassium dichromate oxidation titrimetric method

International Nuclear Information System (INIS)

2004-01-01

This first edition of ISO 7097-1 together with ISO 7097-2:2004 cancels and replaces ISO 7097:1983, which has been technically revised, and ISO 9989:1996. ISO 7097 consists of the following parts, under the general title Nuclear fuel technology - Determination of uranium in solutions, uranium hexafluoride and solids: Part 1: Iron(II) reduction/potassium dichromate oxidation titrimetric method; Part 2: Iron(II) reduction/cerium(IV) oxidation titrimetric method. This part 1. of ISO 7097 describes procedures for the determination of uranium in solutions, uranium hexafluoride and solids. The procedures described in the two independent parts of this International Standard are similar: this part uses a titration with potassium dichromate and ISO 7097-2 uses a titration with cerium(IV)

Contribution to the characterization of the ideality deviation of concentrated solutions of electrolytes: application to the case plutonium and uranium (IV) nitrates

International Nuclear Information System (INIS)

Charrin, N.

1999-01-01

The purpose of this work is to establish a base of binary data referring to the plutonium and uranium nitrates (IV) activity coefficients, which will permit to take account the medium effects in the process of liquid-liquid extraction set in action during the reprocessing of irradiated combustibles in a more scrupulous way. The first chapter sticks to establish the problematic of acquisition of actinides binary data at an oxidation state (IV) linked to two characteristics of this type of electrolyte its radioactive properties and its chemical properties. Its chemical properties bring us to define the fictitious binary data and to use an approach based on the thermodynamic concept of simple solutions, on the measurements of water activity of ternary or quaternary mixtures of the actinide, in nitric acid medium and on the binary data of nitric acid. The second chapter intended to propose reliable binary data concerning nitric acid. The validation of acquisition of fictitious binary data method suggested is undertaken. The electrolyte test is the thorium nitrate (IV). The very encouraging results has determined the carrying out of this work of research in that way. The third chapter is based on the experimental acquisition of uranium and plutonium nitrates (IV) binary data. It emphasises the importance given to the preparation of the studied mixtures which characteristics, very high actinide concentrations and low acidities, make them atypical solutions and without any referenced equivalents. The last chapter describes the exploitation which was made of the established binary data. The characteristic parameters of Pu(NO 3 ) 4 and U(NO 3 ) 4 of Pitzer model and of the specific interaction theory has been appraised. Then the application of' the concept of simple solutions to the calculation of the density or quaternary mixtures like Pu(NO 3 ) 4 / UO 2 (NO 3 ) 2 /HNO 3 / H 2 O was proposed. (author)

Analytical procedure for the titrimetric determination of uranium in concentrates

International Nuclear Information System (INIS)

Florence, T.M.; Pakalns, P.

1989-01-01

In 1964 Davis and gray published a titrimetric method for uranium which does not require column reductors, electronic instruments or inert atmospheres, and is sufficiently selective to enable uranium to be determined without prior separation. The method involves reduction of uranium (VI) to (IV) by ferrous sulphate in concentrated phosphoric acid medium. The excess ion (II) is then selectively oxidised by nitric acid using molybdenum catalyst. After addition of sulphuric acid and dilution with water, the uranium (IV) is titrated with standard potassium dichromate, using barium diphenylamine sulphonate indicator. This method has been found to be simple, precise and reliable, and applicable to a wide range of uranium-containing materials. The method given here for determining uranium in concentrates is essentially that of Davies and Gray. Its applications, apparatus, reagents, procedures and accuracy and precision are discussed. 10 refs

Uranium dioxide pellets

International Nuclear Information System (INIS)

Zawidzki, T.W.

1982-01-01

A process for the preparation of a sintered, high density, large crystal grain size uranium dioxide pellet is described which involves: (i) reacting a uranyl nitrate of formula UO 2 (NO 3 ) 2 .6H 2 O with a sulphur source, at a temperature of from about 300 deg. C to provide a sulphur-containing uranium trioxide; (ii) reacting the thus-obtained modified uranium trioxide with ammonium nitrate to form an insoluble sulphur-containing ammonium uranate; (iii) neutralizing the thus-formed slurry with ammonium hydroxide to precipitate out as an insoluble ammonium uranate the remaining dissolved uranium; (iv) recovering the thus-formed precipitates in a dry state; (v) reducing the dry precipitate to UO 2 , and forming it into 'green' pellets; and (vi) sintering the pellets in a hydrogen atmosphere at an elevated temperature

Heat capacity measurements and XPS studies on uranium-lanthanum mixed oxides

International Nuclear Information System (INIS)

Venkata Krishnan, R.; Mittal, V.K.; Babu, R.; Senapati, Abhiram; Bera, Santanu; Nagarajan, K.

2011-01-01

Research highlights: → Heat capacity measurements were carried out on (U 1-y La y )O 2±x (y = 0.2, 0.4, 0.6, and 0.8) using differential scanning calorimeter (DSC) in the temperature range 298-800 K. → Enthalpy increment measurements were carried out on the above solid solution using high temperature drop calorimetry in the temperature range 800-1800 K. → Chemical states of U and La in the solid solutions of mixed oxides were determined using X-ray photoelectron spectroscopy (XPS). → The anomalous increase in the heat capacity is attributed to certain thermal excitation process namely Frenkel pair defect of oxygen. → From the XPS investigation, it is observed that the O/M ratio at the surface is higher than that to the bulk. → In uranium rich mixed oxide samples, the surface O/M is greater than 2 whereas that in La rich mixed oxides, it is less than 2, though the bulk O/M in all the samples are less than 2. - Abstract: Heat capacity measurements were carried out on (U 1-y La y )O 2±x (y = 0.2, 0.4, 0.6, and 0.8) using differential scanning calorimeter (DSC) in the temperature range 298-800 K. Enthalpy increment measurements were carried out on the above solid solutions using high temperature drop calorimetry in the temperature range 800-1800 K. Chemical states of U and La in the solid solutions of mixed oxides were determined using X-ray photoelectron spectroscopy (XPS). Oxygen to metal ratios of (U 1-y La y )O 2±x were estimated from the ratios of different chemical states of U present in the sample. Anomalous increase in the heat capacity is observed for (U 1-y La y )O 2±x (y = 0.4, 0.6 and 0.8) with onset temperatures in the range of 1000-1200 K. The anomalous increase in the heat capacity is attributed to certain thermal excitation process, namely, Frenkel pair defect of oxygen. The heat capacity value of (U 1-y La y )O 2±x (y = 0.2, 0.4, 0.6, and 0.8) at 298 K are 65.3, 64.1, 57.7, 51.9 J K -1 mol -1 , respectively. From the XPS investigations

Kinetic study of the reduction of Ferric-1, 10-Orthophenanthroline with Uranium (IV) DTPA

International Nuclear Information System (INIS)

Perveen, Rashida; Naqvi, Iftikhar Imam

2006-01-01

The reduction of ferric 1, 10-orthophenanthroline by Uranium (IV) complex of Diethylenetriaminepentaacetic acid was investigated in aqueous hydrochloride acid at 30C, ionic strength 0.01 mole dm-3 and pH 3.5. The mechanism and rate law for the formation of [Fe (opt) 3] was established by isolation method at constant and varying pH values. Spectroscopic method was employed for this investigation. The rate constant and order of reaction with respect to each of the reactant the [U (IV) DTPA] and [Fe(opt3)] was established by plotting a graph 1n (A-At) vs. time. The reaction was observed to be following first order with respect each of following reactants. Overall reaction order was found to be two, having the value of the rate constant 571.59 m min. at pH 3.5. Thermodynamic parameters for the reaction were determined to be E=26.47 kj mol, G=35.11 kj mol, H=24.86 mol and S= 50.17 mol. With the help of Arrhenius equation activation energy for the reaction was calculated. Change in enthalpy and entropy for the reaction (S, H) were determined from the slope and intercept of Eyring plot. Hydrogen ion dependence of the reaction was determined by varying the pH and the rate law was determined. (author)

Uranium determination by spectrophotometry, in chloride solutions, using titanium (III) as reducer; Determinacao de uranio por espectrofotometria, em solucoes cloridricas, utilizando titanio (III) como redutor

Energy Technology Data Exchange (ETDEWEB)

Bastos, E T.R.; Bastos, M B.R.

1986-08-01

A simple method for determining uranium in uranium (VI) solutions with the presence of uranium (IV), iron (II), and titanium (IV) in chloridic solution is described. The method comprises in uranium (VI) reduction with titanium (III), acidity adjustment and uranium (IV) spectrophotometry in hydrochloric acid 2 M. (C.G.C.).

Uranium speciation and stability after reductive immobilization in aquifer sediments

Science.gov (United States)

Sharp, Jonathan O.; Lezama-Pacheco, Juan S.; Schofield, Eleanor J.; Junier, Pilar; Ulrich, Kai-Uwe; Chinni, Satya; Veeramani, Harish; Margot-Roquier, Camille; Webb, Samuel M.; Tebo, Bradley M.; Giammar, Daniel E.; Bargar, John R.; Bernier-Latmani, Rizlan

2011-11-01

It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO 2). In order to explore the form and stability of uranium immobilized under these conditions, we introduced lactate (15 mM for 3 months) into flow-through columns containing sediments derived from a former uranium-processing site at Old Rifle, CO. This resulted in metal-reducing conditions as evidenced by concurrent uranium uptake and iron release. Despite initial augmentation with Shewanella oneidensis, bacteria belonging to the phylum Firmicutes dominated the biostimulated columns. The immobilization of uranium (˜1 mmol U per kg sediment) enabled analysis by X-ray absorption spectroscopy (XAS). Tetravalent uranium associated with these sediments did not have spectroscopic signatures representative of U-U shells or crystalline UO 2. Analysis by microfocused XAS revealed concentrated micrometer regions of solid U(IV) that had spectroscopic signatures consistent with bulk analyses and a poor proximal correlation (μm scale resolution) between U and Fe. A plausible explanation, supported by biogeochemical conditions and spectral interpretations, is uranium association with phosphoryl moieties found in biomass; hence implicating direct enzymatic uranium reduction. After the immobilization phase, two months of in situ exposure to oxic influent did not result in substantial uranium remobilization. Ex situ flow-through experiments demonstrated more rapid uranium mobilization than observed in column oxidation studies and indicated that sediment-associated U(IV) is more mobile than biogenic UO 2. This work suggests that in situ uranium bioimmobilization studies and subsurface modeling parameters should be expanded to account for non-uraninite U(IV) species associated with biomass.

Criticality analysis for mixed thorium-uranium fuel in the Angra-2 PWR reactor using KENO-VI

Energy Technology Data Exchange (ETDEWEB)

Wichrowski, Caio C.; Gonçalves, Isadora C.; Oliveira, Claudio L.; Vellozo, Sergio O.; Baptista, Camila O., E-mail: wichrowski@ime.eb.br, E-mail: isadora.goncalves@ime.eb.br, E-mail: d7luiz@yahoo.com.br, E-mail: vellozo@ime.eb.br, E-mail: camila.oliv.baptista@gmail.com [Instituto Militar de Engenharia (IME), Rio de Janeiro, RJ (Brazil). Seção de Engenharia Nuclear

2017-07-01

The increasing energy demand associated to the current sustainability challenges have given the thorium nuclear fuel cycle renewed interest in the scientific community. Studies have focused on energy production in different reactor designs through the fission of uranium 233, the product of thorium fertilization by neutrons. In order to make it possible for near future applications a strategy based on the adaptation of current nuclear reactors for the use of thorium fuels is being considered. In this work, bearing in mind these limitations, a code was used to evaluate the effect on criticality (k{sub inf}) of the mixing of thorium and uranium in different proportions in the fuel of a PWR, the German designed Angra-2 Brazilian reactor in order to scrutinise its behaviour and determine the feasibility of an adapted ThO{sub 2}-UO{sub 2} mixed fuel cycle using current PWR technology. The analysis is performed using the KENO-VI module in the SCALE 6.1 nuclear safety analysis simulation code and the information is taken from the Angra-2 FSAR (Final Security Analysis Report). (author)

Uranium mining in Australia

International Nuclear Information System (INIS)

Mackay, G.A.

1978-01-01

Western world requirements for uranium based on increasing energy consumption and a changing energy mix, will warrant the development of Australia's resources. By 1985 Australian mines could be producing 9500 tonnes of uranium oxide yearly and by 1995 the export value from uranium could reach that from wool. In terms of benefit to the community the economic rewards are considerable but, in terms of providing energy to the world, Australias uranium is vital

Stripping of Uranium (IV) from D2EHPA + TBP system with ammonium oxalate and its recovery as uranium peroxide

International Nuclear Information System (INIS)

Singh, D.K.; Singh, H.

2014-01-01

Uranium is an important fissile material for the generation of electricity by nuclear reactors. To obtain uranium as a final product meeting the stringent nuclear specifications, many process steps are involved starting from ore processing to the precipitation of yellow cake. Solvent extraction is one of the process industrially adopted worldwide to achieve such purity of uranium from leach liquor and usually uses amine or organophosphorus types of extractant depending upon the composition of feed material. In solvent extraction technique, stripping is a prominent hydrometallurgical operation which brings the metal values of interest in aqueous solution for further treatment. In the case of uranium, stripping is dependent on its oxidation state. For hexavalent state generally carbonate solutions are used, where as in the case of tetravalent form salt solution such as ammonium oxalate is effective. Use of ammonium oxalate as stripping agent for tetravalent uranium from pyrophosphoric acid has been reported in patent however the details are not disclosed. In the present investigation an effort has been made to investigate the stripping behaviour of uranium from a synthetically loaded synergistic solvent mixture of uranium in tetravalent state

Evaluation of an automatic uranium titration system

International Nuclear Information System (INIS)

Lewis, K.

1980-01-01

The titration system utilizes the constant current coulometric titration of Goldbeck and Lerner. U(VI) is reduced to U(IV) by Fe(II). V(V) is generated to titrate the U(IV), and the titration is followed potentiometrically. The evaluation shows that the recovery of uranium is 100% at the 40-mg level. The accuracy is generally +-0.10% or better. The smallest sample weight at which reliable results were obtained was 40 mg of uranium. Time for one analysis is 15 minutes. Advantages and disadvantages of the automated titrator are listed

Uranium in phosphate rocks and future nuclear power fleets

International Nuclear Information System (INIS)

Gabriel, S.; Baschwitz, A.; Mathonniere, G.

2014-01-01

According to almost all forward-looking studies, the world’s energy consumption will increase in the future decades, mostly because of the growing world population and the long-term development of emerging countries. The effort to contain global warming makes it hard to exclude nuclear energy from the global energy mix. Current light water reactors (LWR) burn fissile uranium (a natural, finite resource), whereas some future Generation IV reactors, as Sodium fast reactors (SFR), starting with an initial fissile load, will be capable of recycling their own plutonium and already-extracted depleted uranium. This makes them a feasible solution for the sustainable development of nuclear energy. Nonetheless, a sufficient quantity of plutonium is needed to start up an SFR, with the plutonium already being produced in LWR. The availability of natural uranium therefore has a direct impact on the capacity of the reactors (both LWR and SFR) that we can build. This paper discusses the correspondence between the resources and the nuclear power demand as estimated by various international organisations. Uranium is currently produced from conventional sources. The estimated quantities of uranium evolve over time in relation to their rate of extraction and the discovery of new deposits. Contrary to conventional resources, unconventional resources – because they are hardly used – also exist. These resources are more uncertain both in terms of their quantities and the feasibility of recovering them. Recovering uranium from seawater would guarantee a virtually infinite resource of nuclear fuel, but its technical and economic feasibility has yet to be demonstrated, and huge advances need to be achieved in this direction. According to different publications on phosphate reserves, the potential amount of uranium recoverable from phosphates can be estimated at around 4 MtU. Furthermore, the production of uranium as a by-product of phosphate is determined by the world production of

Indirect determination of uranium by atomic-absorption spectrophotometry using an air-acetylene flame

International Nuclear Information System (INIS)

Alder, J.F.; Das, B.C.

1977-01-01

An indirect method has been developed for the determination of uranium by atomic-absorption spectrophotometry using an air-acetylene flame. Use is made of the reduction of copper(II) by uranium(IV) followed by complex formation of the copper(I) ions so produced with neocuproine (2,9-dimethyl-1,10-phenanthroline) and finally the determination of copper in this complex by atomic-absorption spectrophotometry. The results show that the method can be recommended, provided that care is taken to ensure the complete reduction of uranium(VI) to uranium(IV). The sensitivity of the method is 4.9 μg of uranium and the upper limit 500 μg without dilution. (author)

Yellowcake: the international uranium cartel

International Nuclear Information System (INIS)

Taylor, J.H.; Yokell, M.D.

1979-01-01

The dramatic events that occurred in the uranium market between 1972 and 1976, and their repercussions is discussed. In particular, the book concentrates on the international uranium cartel's attempt to fix yellowcake prices. The background of the yellowcake industry is discussed in Part I of the book, and the demand for uranium and the nuclear fuel cycle isdiscussed, along with a brief anecdotal history of the uranium industry. Part II describes the political conflicts in Australia which led to the public exposure of the uranium cartel and the situation in the world uranium market that led to the cartel's formation. The legal repercussions of the cartel's exposure are discussed in Part III, and in Part IV, the authors reflect on the ramifications of the events described in the book and some of the issues they raise

Sorption of Uranium(VI) and Thorium(IV) ions from aqueous solutions by nano particle of ion exchanger SnO2

International Nuclear Information System (INIS)

Nilchi, A.; Rasouli Garmarodi, S.; Shariati Dehaghan, T.

2012-01-01

Due to the extensive use of nuclear energy and its replacement for fossil fuels in recent decades, the radioactive waste production has increased enormously. The vast majority of the radioactive wastes products, are in the liquid form and consequently their treatment is of great importance. In this paper, tin oxide with nano-structure has been synthesized as an absorbent by the homogenous sedimentation method in the presence of urea, so as to adsorb uranium(VI) and thorium(IV) ions. The results obtained from the XRD, Scanning Electron Microscopy and nitrogen adsorption/ desorption analyses on the tin oxide sample showed the cassiterite structure with an average particle size of 30 nanometer and a specific surface area of 27.5 m 2 /g. The distribution coefficients of uranium and thorium were studied by means of batch method. The effects of different variables such as pH and time of contact between the exchanger and solution were investigated and the optimum conditions for sorption of these ions were determined.

Bioreduction of Uranium(VI) Complexed with Citric Acid by Clostridia Affects its Structure and Mobility

International Nuclear Information System (INIS)

Francis, A.; Dodge, C.

2008-01-01

Uranium contamination of the environment from mining and milling operations, nuclear-waste disposal, and ammunition use is a widespread global problem. Natural attenuation processes such as bacterial reductive precipitation and immobilization of soluble uranium is gaining much attention. However, the presence of naturally occurring organic ligands can affect the precipitation of uranium. Here, we report that the anaerobic spore-forming bacteria Clostridia, ubiquitous in soils, sediments, and wastes, capable of reduction of Fe(III) to Fe(II), Mn(IV) to Mn(II), U(VI) to U(IV), Pu(IV) to Pu(III), and Tc(VI) to Tc(IV); reduced U(VI) associated with citric acid in a dinuclear 2:2 U(VI):citric acid complex to a biligand mononuclear 1:2 U(IV):citric acid complex, which remained in solution, in contrast to reduction and precipitation of uranium. Our findings show that U(VI) complexed with citric acid is readily accessible as an electron acceptor despite the inability of the bacterium to metabolize the complexed organic ligand. Furthermore, it suggests that the presence of organic ligands at uranium-contaminated sites can affect the mobility of the actinide under both oxic and anoxic conditions by forming such soluble complexes.

Separation of uranium from (Th,U)O2 solid solutions

International Nuclear Information System (INIS)

Chiotti, P.; Jha, M.C.

1976-01-01

Uranium is separated from mixed oxides of thorium and uranium by a pyrometallurgical process in which the oxides are mixed with a molten chloride salt containing thorium tetrachloride and thorium metal which reduces the uranium oxide to uranium metal which can then be recovered from the molten salt. The process is particularly useful for the recovery of uranium from generally insoluble high-density sol-gel thoria-urania nuclear reactor fuel pellets. 7 claims

Towards new developments in uranium chemistry. Scientific report presented to obtain and Accreditation to Supervise Research

International Nuclear Information System (INIS)

Berthet, Jean-Claude

2003-01-01

After a presentation of his academic curriculum, the author proposes an overview of some of his main research activities and works which notably addressed the reactivity of uranium III complexes (synthesis and reactivity of uranium hydride complexes, synthesis of poly-metallic complexes), amide complexes (synthesis of uranium IV amide precursors, reactivity of cationic complexes, synthesis of uranium IV complexes), uranium triflate (or trifluoromethanesulfonate) complexes, the synthesis of U(Cot)X_2(L)_n complexes and of their derivatives, the complexing of lanthanide iodides and triflates

Anaerobic bacterial systems result in the removal of soluble uranium

International Nuclear Information System (INIS)

Thomson, B.M.; Barton, L.L.; Steenhoudt, K.; Tucker, M.D.

1994-01-01

Sulfate-reducing bacteria, nitrate-reducing bacteria and bacteria present in sewage sludge were examined for their ability to reduce the level of soluble U(VI) in enriched media. Cultures of Desulfovibrio desulfuricans, D. gigas, and D. vulgaris were grown in sulfate-containing media while Pseudomonas putida and P. denitrificans were cultivated in nitrate media. The amount of U(VI) removed from solution was dependent on metabolism because greater levels of uranium were removed when U(VI) was added to a growing culture than when added to a culture in stationary phase. The presence of vanadate, arsenate, selenate or molybdate at 0.1 and 0.01 M levels in sulfate-reducing cultures, nitrate-respiring cultures or in sludge cultures did not have an effect on the amount of uranium removed. In all cultures the amount of uranium in solution was markedly reduced after 10 to 20 days and reduced uranium, as U(IV), was detected in several cultures. Present in the cultures of D. desulfuricans were crystals of uranium. Examination of these cultures by electron microscopy indicates that the uranium (IV) is deposited outside of the cell and these needle-like crystals are associated with cellular material. X-ray probe analysis with the electron microscope gave an image that was in close agreement with U(IV). With D. desulfuricans in a continuous stirred tank reactor, kinetic parameters have been calculated for uranium reduction. Over a period of 20 to 60 hours, the amount of soluble uranium removed from the bioreactor was proportional to residence time over a period of 20 to 60 hours

Coordination and solvent extraction behaviour of oxozirconium(IV), thorium(IV) and dioxouranium(VI)

International Nuclear Information System (INIS)

Dash, K.C.

1989-01-01

The systematic liquid-liquid extraction behaviour of oxozirconium (IV), thorium(IV) and dioxouranium(VI) have been investigated using a number of synthesised and commercial chelating extractants. The synergism or antagonism for these processes in presence of neutral donor ligands have also been identified and the conditions for separation and isolation of pure individual metal ions have been established. The coordination behaviour of oxozirconium(IV), thorium(IV) and dioxouranium(VI) with a large number of mono- and polydentate ligands have been studied. With oxozirconium(IV), invariably always a cyclic, tetranuclear species is obtained, derived from the tetrameric structure of the parent ZrOCl 2 .8H 2 O which is actually (Zr 4 (OH) 8 (H 2 O) 16 )Cl 8 .12H 2 O. No simple, monomeric oxozirconium(IV) complex was obtained. Uranium(VI) and thorium(IV) form a wide variety of complexes of higher coordination numbers and several bi- and trinuclear complexes were also characterised where the two adjacent metal centres are joined to each other by a double hydroxo-bridge. (author). 69 refs., 3 figs., 4 tabs

Fundamental study on decontamination of wastes contaminated by uranium fluorides by using ionic liquids - dissolution and electrochemistry of uranium in 1-butyl-3-methylimidazolium chloride

International Nuclear Information System (INIS)

Noriko Asanuma; Yusuke Ohhashi; Yukio Wada; Masayuki Harada; Yasuhisa Ikeda

2008-01-01

Treatment method for wastes contaminated uranium fluorides by using ionic liquids as media of pyrochemical process instead of alkali metal chloride molten salts was proposed. In this method, uranium fluorides such as UF 4 or NaF adsorbing UF 6 are dissolved in 1-butyl-3-methylimidazolium chloride (BMICl) and dissolved uranium species are recovered as deposits by electrochemical reduction. Under the atmospheric condition, UF 4 was completely dissolved in BMICl at 100 deg. C. UV-vis absorption spectra of the sample solution indicated that main species of uranium are U(VI) and a part of uranium exists as U(IV). Chemical form of uranium in the NaF adsorbents is Na 3 UO 2 F 5 . Therefore, it was immediately dissolved to BMICl. However, complete dissolution was not achieved. Cyclic voltammetry of the solutions prepared by dissolution experiments was performed. Redox properties of uranium species in each sample were irreversible. It was assigned to reduction of U(VI) to U(IV). As a result of preliminary bulk electrolysis, it was expected that reduction products are deposited on the carbon cathode. (authors)

Retention and reduction of uranium on pyrite surface

International Nuclear Information System (INIS)

Eglizaud, N.

2006-12-01

In the hypothesis of a storage of the spent fuel in a deep geological formation, understanding the uranium dispersion in the environment is important. Pyrite is a reducing mineral present in the Callovo-Oxfordian argilites, the geological formation actually studied for such a storage. However, pyrite impact on uranium migration has already been poorly studied. The aim of the study was to understand the mechanisms of uranium(VI) retention and reduction on the pyrite surface (FeS 2 ). Solution chemistry was therefore coupled with solid spectroscopic studies (XPS and Raman spectroscopy). All uranium-pyrite interactions experiments were performed under an anoxic atmosphere, in a glove box. Pyrite dissolution under anoxic conditions releases sulfoxy-anions and iron(II), which can then be adsorbed on the pyrite surface. This adsorption was confirmed by interaction experiments using iron(II) isotopic dilution. Uranium(VI) is retained by an exchange reaction with iron(II) adsorbed on sulphur sites, with a maximal amount of sorbed uranium at pH ≥ 5.5. Cobalt(II) and europium(III) are also adsorbed on the pyrite surface above pH 5.5 confirming then that reduction is not required for species to adsorb on pyrite. When the concentration of uranium retained is lower than 4 x 10 -9 mol g -1 , an oxidation-reduction reaction leads to the formation of a uranium (VI) (IV) mixed oxide and to solid sulphur (d.o. ≥ -I). During this reaction, iron remains mostly at the +II oxidation degree. The reaction products seem to passivate the pyrite surface: at higher amounts of retained uranium, the oxidation-reduction reaction is no longer observed. The surface is saturated by the retention of (3.4 ± 0.8) x 10 -7 mol L -1 of uranium(VI). Modelling of uranium sorption at high surface coverage (≥ 4 x 10 -9 mol g -1 ) by the Langmuir model yields an adsorption constant of 8 x 10 7 L mol -1 . Finally, a great excess of uranium(VI) above the saturation concentration allows the observation of

Remediation of uranium contaminated soils with bicarbonate extraction and microbial U(VI) reduction

International Nuclear Information System (INIS)

Phillips, E.J.P.; Landa, E.R.; Lovley, D.R.

1995-01-01

A process for concentrating uranium from contaminated soils in which the uranium is first extracted with bicarbonate and then the extracted uranium is precipitated with U(VI)-reducing microorganisms was evaluated for a variety of uranium-contaminated soils. Bicarbonate (100 mM) extracted 20-94% of the uranium that was extracted with nitric acid. The U(VI)-reducing microorganism, Desulfovibrio desulfuricans reduced the U(VI) to U(IV) in the bicarbonate extracts. In some instances unidentified dissolved extracted components, presumably organics, gave the extract a yellow color and inhibited U(VI) reduction and/or the precipitation of U(IV). Removal of the dissolved yellow material with the addition of hydrogen peroxide alleviated this inhibition. These results demonstrate that bicarbonate extraction of uranium from soil followed by microbial U(VI) reduction might be an effective mechanism for concentrating uranium from some contaminated soils. (author)

Retention and reduction of uranium on pyrite surface; Retention et reduction de l'uranium a la surface de la pyrite

Energy Technology Data Exchange (ETDEWEB)

Eglizaud, N

2006-12-15

In the hypothesis of a storage of the spent fuel in a deep geological formation, understanding the uranium dispersion in the environment is important. Pyrite is a reducing mineral present in the Callovo-Oxfordian argilites, the geological formation actually studied for such a storage. However, pyrite impact on uranium migration has already been poorly studied. The aim of the study was to understand the mechanisms of uranium(VI) retention and reduction on the pyrite surface (FeS{sub 2}). Solution chemistry was therefore coupled with solid spectroscopic studies (XPS and Raman spectroscopy). All uranium-pyrite interactions experiments were performed under an anoxic atmosphere, in a glove box. Pyrite dissolution under anoxic conditions releases sulfoxy-anions and iron(II), which can then be adsorbed on the pyrite surface. This adsorption was confirmed by interaction experiments using iron(II) isotopic dilution. Uranium(VI) is retained by an exchange reaction with iron(II) adsorbed on sulphur sites, with a maximal amount of sorbed uranium at pH {>=} 5.5. Cobalt(II) and europium(III) are also adsorbed on the pyrite surface above pH 5.5 confirming then that reduction is not required for species to adsorb on pyrite. When the concentration of uranium retained is lower than 4 x 10{sup -9} mol g{sup -1}, an oxidation-reduction reaction leads to the formation of a uranium (VI) (IV) mixed oxide and to solid sulphur (d.o. {>=} -I). During this reaction, iron remains mostly at the +II oxidation degree. The reaction products seem to passivate the pyrite surface: at higher amounts of retained uranium, the oxidation-reduction reaction is no longer observed. The surface is saturated by the retention of (3.4 {+-} 0.8) x 10{sup -7} mol L{sup -1} of uranium(VI). Modelling of uranium sorption at high surface coverage ({>=} 4 x 10{sup -9} mol g{sup -1}) by the Langmuir model yields an adsorption constant of 8 x 10{sup 7} L mol{sup -1}. Finally, a great excess of uranium(VI) above the

Simultaneous determination of a binary mixture: kinetic method for determination of uranium and vanadium

International Nuclear Information System (INIS)

Jianhua, W.; Ronghuan, H.

1993-01-01

A kinetic method for simultaneous determination of a binary mixture is proposed, and a procedure for simultaneous determination of uranium (IV) and vanadium (IV) is established based on their inductive effect on chromium (VI)-iodide redox reaction in a weak acidic medium. The reaction was monitored by FIA-spectrophotometry using the I 3 - -starch complex as indicator. The calibration graphs are linear for uranium (IV) and vanadium (IV) within the range of 0 ∼ 3.6 μg/ml and 0 ∼ 2.5 μg/ml respectively. Most foreign ions, except for iron (II) and antimony (III), do not interfere with the determination. The uranium and vanadium content in different samples was determined, and the results were satisfactory. (author). 2 tabs., 2 figs., 9 refs

A metallogenetic model of supergene extraction, releasing and enrichment in the mixed zone for granite-type uranium deposits in south China

International Nuclear Information System (INIS)

Li Minglian.

1986-01-01

The major geological features and their related geological events provide a base for the modelling of granite-type uranium deposits in South China. This paper presents a metallogenetic model to suggest the process of ore fluid circulation. There are two streams of ore fluids moving in the fracture zone: one comes from meteoric water and extracts uranium from wall rocks, flowing from top to bottom which is named uranium-loading fluid; another derives from the depth of the crust flowing from bottom to top and contains reducing matters as H 2 S etc. called uranium-releasing fluid. These two streams of solutions of different genesis, composition and character encountered and mixed at certain depth to precipitate the uranium. During the process the longitudinal circulation of underground thermal water in fracture zone results in the Bernoulli latitudinal circulation of ore fluids, which caused the ore fluids to ceaselessly flow into the minerogenetic location, where mineralization can be formed continuously in a certain period

Feasibility studies on electrochemical recovery of uranium from solid wastes contaminated with uranium using 1-butyl-3-methylimidazorium chloride as an electrolyte

Energy Technology Data Exchange (ETDEWEB)

Ohashi, Yusuke, E-mail: ohhashi.yusuke@jaea.go.jp [Ningyo-toge Environmental Engineering center, Japan Atomic Energy Agency, 1550 Kamisaibara, Kagamino-cho, Tomata-gun, Okayama 708-0698 (Japan); Harada, Masayuki [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1-N1-34 Ookayama, Meguro-ku, Tokyo 152-8550 (Japan); Asanuma, Noriko [Department of Nuclear Engineering, School of Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka-shi, Kanagawa 259-1292 (Japan); Ikeda, Yasuhisa [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1-N1-34 Ookayama, Meguro-ku, Tokyo 152-8550 (Japan)

2015-09-15

Highlights: • The uranium component of steel wastes and spent NaF adsorbent are easily dissolved into BMICl. • The uranyl(VI) species in BMICl are reduced to U(V) irreversibly around −0.8 to −1.3 V. • The dissolved uranium species in BMICl are recovered as black deposits electrolytically. • The deposit is the mixtures of U(IV) and U(VI) compounds containing O, F, Cl, and N elements. - Abstract: In order to examine feasibility of the electrochemical deposition method for recovering uranium from the solid wastes contaminated with uranium using ionic liquid as electrolyte, we have studied the electrochemical behavior of each solution prepared by soaking the spent NaF adsorbents and the steel waste contaminated with uranium in BMICl (1-butyl-3-methyl- imidazolium chloride). The uranyl(VI) species in BMICl solutions were found to be reduced to U(V) irreversibly around −0.8 to −1.3 V vs. Ag/AgCl. The resulting U(V) species is followed by disproportionation to U(VI) and U(IV). Based on the electrochemical data, we have performed potential controlled electrolysis of each solution prepared by soaking the spent NaF adsorbents and steel wastes in BMICl at −1.5 V vs. Ag/AgCl. Black deposit was obtained, and their composition analyses suggest that the deposit is the mixtures of U(IV) and U(VI) compounds containing O, F, Cl, and N elements. From the present study, it is expected that the solid wastes contaminated with uranium can be decontaminated by treating them in BMICl and the dissolved uranium species are recovered electrolytically.

Liquid-liquid extraction and separation studies of uranium(VI)

International Nuclear Information System (INIS)

Langade, A.D.; Shinde, V.M.

1980-01-01

Separation of uranium(VI) from iron(III), molybdenum(VI), vanadium(V), bismuth(III), zirconium(IV) and thorium(IV) is achieved by liquid-liquid extraction with 4-methyl-3-pentene-2-one (mesityl oxide; MeO) from sodium salicylate media (0.1M, pH 6.0). The extracted species is UO 2 (HO.C 6 H 4 COO) 2 .2MeO. A procedure for separating 50 μg of uranium from mg amounts of the other metals is described. (author)

Activation of chalcogens and chalcogenides at reactive uranium centers

Energy Technology Data Exchange (ETDEWEB)

Franke, Michael Sebastian

2015-07-23

The high reactivity of many trivalent uranium complexes was investigated in the Meyer group, however, these studies were not limited to small-molecule activation, but were extended to other relatively inert reagents like the heavier elemental chalcogens sulfur, selenium, and tellurium. The tripodal N-anchored chelate ({sup Ad,Me}ArO){sub 3}N{sup 3-} (trianion of tris(3-Adamantyl-2-hydroxy-5-methylbenzyl)amine) was found to be a very suitable candidate for this task and the respective uranium(III) complex [(({sup Ad,Me}ArO){sub 3}N)U{sup III}(DME)] is able to activate elemental sulfur and selenium to form the dinuclear, chalcogenido-bridged complexes [{(("A"d","M"eArO)_3N)U"I"V(DME)}{sub 2}(μ-E)] (E = S, Se). Starting from this previously accomplished work, research in this thesis aimed at furthering reactivity studies of trivalent [(({sup Ad,Me}ArO){sub 3}N)U{sup III}(DME)], but also its chalcogenido-bridged uranium(IV) products, and the spectroscopic characterization of all newly synthesized compounds. Furthermore, the development of the new phenol HOAr* (Ar* = 2,6-(CHPh{sub 2}){sub 2}-4-Me-C{sub 6}H{sub 2}, 2,6-bis(diphenylmethyl)-4-methylphenyl) and its establishment as a ligand to be used for uranium coordination chemistry was another goal of this thesis. The activation of CO{sub 2} by uranium(III) complex [(({sup Ad,Me}ArO){sub 3}N)U{sup III}(DME)] to yield the dinuclear, carbonate-bridged uranium(IV/IV) complex [{(("A"d","M"eArO)_3N)U"I"V(DME)}{sub 2}(μ-κ{sup 1}:κ{sup 2}-CO{sub 3})] and CO was reported in 2010 by Meyer and co-workers. These previous results led to the pursuit of the isolation of mixed chalcogenocarbonate complexes from the reaction of the bridging chalcogenidos [{(("A"d","M"eArO)_3N)U"I"V(DME)}{sub 2}(μ-E)] (E = S, Se) with either CO{sub 2} or its heterocumulene analogs COS or CS{sub 2}. The chalcogeno-carbonates [{(("A"d","M"eArO)_3N)U"I"V(DME)}{sub 2}(μ-κ{sup 1}:κ{sup 2}-CO{sub 2}E)] und [{(("A"d","M"eArO)_3N)U"I"V-(DME)}{sub 2}(�

Uranium Bio-accumulation and Cycling as revealed by Uranium Isotopes in Naturally Reduced Sediments from the Upper Colorado River Basin

Science.gov (United States)

Lefebvre, Pierre; Noël, Vincent; Jemison, Noah; Weaver, Karrie; Bargar, John; Maher, Kate

2016-04-01

Uranium (U) groundwater contamination following oxidized U(VI) releases from weathering of mine tailings is a major concern at numerous sites across the Upper Colorado River Basin (CRB), USA. Uranium(IV)-bearing solids accumulated within naturally reduced zones (NRZs) characterized by elevated organic carbon and iron sulfide compounds. Subsequent re-oxidation of U(IV)solid to U(VI)aqueous then controls the release to groundwater and surface water, resulting in plume persistence and raising public health concerns. Thus, understanding the extent of uranium oxidation and reduction within NRZs is critical for assessing the persistence of the groundwater contamination. In this study, we measured solid-phase uranium isotope fractionation (δ238/235U) of sedimentary core samples from four study sites (Shiprock, NM, Grand Junction, Rifle and Naturita, CO) using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS). We observe a strong correlation between U accumulation and the extent of isotopic fractionation, with Δ238U up to +1.8 ‰ between uranium-enriched and low concentration zones. The enrichment in the heavy isotopes within the NRZs appears to be especially important in the vadose zone, which is subject to variations in water table depth. According to previous studies, this isotopic signature is consistent with biotic reduction processes associated with metal-reducing bacteria. Positive correlations between the amount of iron sulfides and the accumulation of reduced uranium underline the importance of sulfate-reducing conditions for U(IV) retention. Furthermore, the positive fractionation associated with U reduction observed across all sites despite some variations in magnitude due to site characteristics, shows a regional trend across the Colorado River Basin. The maximum extent of 238U enrichment observed in the NRZ proximal to the water table further suggests that the redox cycling of uranium, with net release of U(VI) to the groundwater by

Calibration Tools for Measurement of Highly Enriched Uranium in Oxide and Mixed Uranium-Plutonium Oxide with a Passive-Active Neutron Drum Shuffler

International Nuclear Information System (INIS)

Mount, M; O'Connell, W; Cochran, C; Rinard, P

2003-01-01

Lawrence Livermore National Laboratory (LLNL) has completed an extensive effort to calibrate the LLNL passive-active neutron drum (PAN) shuffler (Canberra Model JCC-92) for accountability measurement of highly enriched uranium (HEU) oxide and HEU in mixed uranium-plutonium (U-Pu) oxide. Earlier papers described the PAN shuffler calibration over a range of item properties by standards measurements and an extensive series of detailed simulation calculations. With a single normalization factor, the simulations agree with the HEU oxide standards measurements to within ±1.2% at one standard deviation. Measurement errors on mixed U-Pu oxide samples are in the ±2% to ±10% range, or ±20 g for the smaller items. The purpose of this paper is to facilitate transfer of the LLNL procedure and calibration algorithms to external users who possess an identical, or equivalent, PAN shuffler. Steps include (1) measurement of HEU standards or working reference materials (WRMs); (2) MCNP simulation calculations for the standards or WRMs and a range of possible masses in the same containers; (3) a normalization of the calibration algorithms using the standard or WRM measurements to account for differences in the 252 Cf source strength, the delayed-neutron nuclear data, effects of the irradiation protocol, and detector efficiency; and (4) a verification of the simulation series trends against like LLNL results. Tools include EXCEL/Visual Basic programs which pre- and post-process the simulations, control the normalization, and embody the calibration algorithms

Haematological malignancies in childhood in Croatia: Investigating the theories of depleted uranium, chemical plant damage and 'population mixing'

International Nuclear Information System (INIS)

Labar, B.; Rudan, I.; Ivankovic, D.; Biloglav, Z.; Mrsic, M.; Strnad, M.; Fucic, A.; Znaor, A.; Bradic, T.; Campbell, H.

2004-01-01

Some of potential causes proposed to explain the reported increase of haematological malignancies in childhood during or after the war period in several countries include depleted uranium, chemical pollution and population mixing theory. The aim of this study was to define the population of Croatian children aged 0-14 years who were potentially exposed to each of those risks during the war and to investigate any possible association between the exposure and the incidence of haematological malignancies. The authors analyzed the data reported by the Cancer Registry of Croatia during the pre-war period (1986-1990), war period (1991-1995) and post-war period (1996-1999). In the group of 10 counties potentially exposed to depleted uranium and two counties where chemical war damage occurred, no significant difference in incidence of the studied haematological malignancies was noted in comparison to pre-war period. The incidence of lymphatic leukaemia significantly increased in four counties where population mixing had occurred during the war period, supporting the 'mixing theory'. In those counties, the incidence of Hodgkin's lymphoma decreased during and after the war. In Croatia as a whole, decreases in incidence of myeloid leukaemias during war and non-Hodgkin lymphoma after the war were noted

Titrimetric determination of uranium in tributyl phosphate

International Nuclear Information System (INIS)

Sobkowska, A.

1978-01-01

The titrimetric method involving the reduction of U(VI) to uranium(IV) by iron(II) in phosphoric acid, selective oxidation of the excess of iron(II) and potentiometric titration with dichromate was directly used for the determination of uranium in tributyl phosphate mixtures. The procedure was applied to solutions containing more than 2 mg of uranium in the sample but the highest precision and accuracy were obtained in the range from 20 to 200 mg of uranium. Dibutyl phosphate and monobutyl phosphate as well as the other radiolysis products of TBP had no influence on the results of determinations. (author)

Law of substitution for mixed arrays

International Nuclear Information System (INIS)

Koudelka, A.J.

1987-01-01

The nuclear safety justification of a mixed array of dissimilar fissile units of metal units and dilute solution units, according to Clayton, has been a persistent and nagging problem. Dissimilar uranium metal or dissimilar uranium solution units in a mixed array can also create a modeling nightmare for the nuclear criticality safety engineer. Now, a calculational method known as the Law of Substitution has been developed to ensure that the k/sub eff/ of an array of uranium metal and uranium solution units will satisfy any k/sub eff/ limit set by the nuclear safety engineer. The nuclear criticality safety engineer can utilize the Law of Substitution to safely mix or substitute different uranium metal units, different uranium solution units, and more importantly, uranium metal and dilute UO 2 solution units in an array. The Law of Substitution is as follows: (1) calculate the k/sub eff/ of each unit type in its own infinite planar array. (2) Determine the edge-to-edge spacing of the infinite planar array of each type of unit to satisfy a desired k/sub eff/. (3) Select the largest edge-to-edge spacing from among the similar units in their infinite planar arrays and use that spacing for the finite or infinite planar array of mixed units

Fundamental study on decontamination of wastes contaminated by uranium fluorides by using ionic liquids - dissolution and electrochemistry of uranium in 1-butyl-3-methylimidazolium chloride

Energy Technology Data Exchange (ETDEWEB)

Noriko Asanuma [Department of Energy Science and Engineering, School of Engineering, Tokai University 1117 Kitakaname, Hiratsuka-shi, Kanagawa 259-1292 (Japan); Yusuke Ohhashi; Yukio Wada [Ningyo-toge Environmental Engineering Center, Japan Atomic Energy Agency Kagamino-cho, Tomata-gun, Okayama 708-0698 (Japan); Masayuki Harada; Yasuhisa Ikeda [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology 2-12-1-N1-34 Ookayama, Meguro-ku, Tokyo 152-8550 (Japan)

2008-07-01

Treatment method for wastes contaminated uranium fluorides by using ionic liquids as media of pyrochemical process instead of alkali metal chloride molten salts was proposed. In this method, uranium fluorides such as UF{sub 4} or NaF adsorbing UF{sub 6} are dissolved in 1-butyl-3-methylimidazolium chloride (BMICl) and dissolved uranium species are recovered as deposits by electrochemical reduction. Under the atmospheric condition, UF{sub 4} was completely dissolved in BMICl at 100 deg. C. UV-vis absorption spectra of the sample solution indicated that main species of uranium are U(VI) and a part of uranium exists as U(IV). Chemical form of uranium in the NaF adsorbents is Na{sub 3}UO{sub 2}F{sub 5}. Therefore, it was immediately dissolved to BMICl. However, complete dissolution was not achieved. Cyclic voltammetry of the solutions prepared by dissolution experiments was performed. Redox properties of uranium species in each sample were irreversible. It was assigned to reduction of U(VI) to U(IV). As a result of preliminary bulk electrolysis, it was expected that reduction products are deposited on the carbon cathode. (authors)

Remediation of uranium contaminated soils with bicarbonate extraction and microbial U(VI) reduction

Science.gov (United States)

Philips , Elizabeth J.P.; Landa, Edward R.; Lovely, Derek R.

1995-01-01

A process for concentrating uranium from contaminated soils in which the uranium is first extracted with bicarbonate and then the extracted uranium is precipitated with U(VI)-reducing microorganisms was evaluated for a variety of uranuum-contaminated soils. Bicarbonate (100 mM) extracted 20–94% of the uranium that was extracted with nitric acid. The U(VI)-reducing microorganism,Desulfovibrio desulfuricans reduced the U(VI) to U(IV) in the bicarbonate extracts. In some instances unidentified dissolved extracted components, presumably organics, gave the extract a yellow color and inhibited U(VI) reduction and/or the precipitation of U(IV). Removal of the dissolved yellow material with the addition of hydrogen peroxide alleviated this inhibition. These results demonstrate that bicarbonate extraction of uranium from soil followed by microbial U(VI) reduction might be an effective mechanism for concentrating uranium from some contaminated soils.

Plutonium separation by reduction stripping. Application to processing of mixed oxide (U,Pu)O2 fuel fabrication wastes

International Nuclear Information System (INIS)

Arnal, Thierry; Cousinou, Gerard; Ganivet, Michel.

1978-11-01

A procedure is described for separating plutonium from a uranium VI and plutonium IV mixture contained in an organic phase (tributyl phosphate diluted in dodecane). This separation is obtained by extracting the plutonium III using two organic reducers: hydrazine and paraminophenol. Paraminophenol has excellent reducing qualities, similar to those of ferrous sulphamate, but has the added advantage of not contaminating extracted plutonium. This procedure is currently used in processing production wastes from mixed oxide (U,Pu)O 2 fuels; the installation using this procedure is described in detail in this paper. Operating results show the remarkable efficiency of this procedure: the separated plutonium and uranium mass flows have been increased to 185 and 350 g.h -1 respectively; the uranium contains less than 0.1 ppm of plutonium on completion of the purification cycle [fr

Extraction of Tetravalent Uranium by Certain Acidic Organophosphorus Extractants from Phosphate Medium

International Nuclear Information System (INIS)

Daoud, J.A.; Zeid, M.M.; Aly, H.F.

1998-01-01

The extraction of U(IV) by octylphenyl acid phosphate (OPAP) or di-2-ethylhexyl phosphoric acid (HDEHP) in kerosene from phosphoric acid was carried out. The effect of extractant, phosphoric acid, uranium, Fe(II) and Fe(III) concentration on the extraction process was separately investigated. The effect of different reagents and temperature on the stripping of U(IV) was also investigated. The results obtained for the extraction of U(IV) by HDEHP showed that the extraction with the increase in HDEHP and Fe(III) concentration while it decreases with the increase in phosphoric acid, uranium and Fe(II) concentration. In case of extraction with OPAP, the extraction of U(IV) was found to decrease with the phosphoric acid, Fe(II) and initial uranium concentration while the increase in OPAP concentration slightly affected the extraction. The use of high phosphoric acid concentration as stripper at low temperature was found to give the best stripping results

Sorption of uranium by clinoptilolite modified by a some metals hydroxides

International Nuclear Information System (INIS)

Plotnikov, V.I.; Medvedeva, Z.V.; Zhabykbaev, G.T.

2005-01-01

In the present report the sorption character of uranium (IV) in the static conditions on the thin layer sorbents with application of the clinoptilolite of the Chankan deposit of the Republic of Kazakhstan is shown. A wide circle of metal hydroxides - in both the individual form and in the their mixture - is used. It is shown that the most sorptive capacity against the uranium (IV) has the modified clinoptilolite of MnO 2

Process for producing uranium oxide rich compositions from uranium hexafluoride

International Nuclear Information System (INIS)

DeHollander, W.R.; Fenimore, C.P.

1978-01-01

Conversion of gaseous uranium hexafluoride to a uranium dioxide rich composition in the presence of an active flame in a reactor defining a reaction zone is achieved by separately introducing a first gaseous reactant comprising a mixture of uranium hexafluoride and a reducing carrier gas, and a second gaseous reactant comprising an oxygen-containing gas. The reactants are separated by a shielding gas as they are introduced to the reaction zone. The shielding gas temporarily separates the gaseous reactants and temporarily prevents substantial mixing and reacting of the gaseous reactants. The flame occurring in the reaction zone is maintained away from contact with the inlet introducing the mixture to the reaction zone. After suitable treatment, the uranium dioxide rich composition is capable of being fabricated into bodies of desired configuration for loading into nuclear fuel rods. Alternatively, an oxygen-containing gas as a third gaseous reactant is introduced when the uranium hexafluoride conversion to the uranium dioxide rich composition is substantially complete. This results in oxidizing the uranium dioxide rich composition to a higher oxide of uranium with conversion of any residual reducing gas to its oxidized form

Final Project Report, DE-SC0001280, Characterizing the Combined Roles of Iron and Transverse Mixing on Uranium Bioremediation in Groundwater using Microfluidic Devices

Energy Technology Data Exchange (ETDEWEB)

Finneran, Kevin [Clemson Univ., SC (United States); Werth, Charles [Univ. of Texas, Austin, TX (United States); Strathmann, Timothy [Univ. of Illinois, Urbana-Champaign, IL (United States)

2015-01-10

In situ bioremediation of U(VI) involves amending groundwater with an appropriate electron donor and limiting nutrients to promote biological reduction to the less soluble and mobile U(IV) oxidation state. Groundwater flow is laminar; mixing is controlled by hydrodynamic dispersion. Recent studies indicate that transverse dispersion along plume margins can limit mixing of the amended electron donor and accepter (such as U(VI) in remediation applications). As a result, microbial growth, and subsequently contaminant reaction, may be limited to these transverse mixing zones during bioremediation. The primary objective of this work was to characterize the combined effects of hydrology, geochemistry, and biology on the (bio)remediation of U(VI). Our underlying hypothesis was that U(VI) reaction in groundwater is controlled by transverse mixing with an electron donor along plume margins, and that iron bioavailability in these zones affects U(VI) reduction kinetics and U(IV) re-oxidation. Our specific objectives were to a) quantify reaction kinetics mediated by biological versus geochemical reactions leading to U(VI) reduction and U(IV) re-oxidation, b) understand the influence of bioavailable iron on U(VI) reduction and U(IV) re-oxidation along the transverse mixing zones, c) determine how transverse mixing limitations and the presence of biomass in pores affects these reactions, and d) identify how microbial populations that develop along transverse mixing zones are influenced by the presence of iron and the concentration of electron donor. In the completed work, transverse mixing zones along plume margins were re-created in microfluidic pore networks, referred to as micromodels. We conducted a series of experiments that allowed us to distinguish among the hydraulic, biological, and geochemical mechanisms that contribute to U(VI) reduction, U(IV) re-oxidation, and U(VI) abiotic reaction with the limiting biological nutrient HP042-. This systematic approach may lead to a

Determination of plutonium and uranium in the same aliquot by potentiometric titration

International Nuclear Information System (INIS)

Karekar, C.V.; Chander, Keshav; Nair, G.M.; Natarajan, P.R.

1986-01-01

A potentiometric titration method was developed for the determination of plutonium and uranium in the same aliquot in nitric acid medium. Plutonium was first determined by oxidation to Pu(VI) by fuming with HClO 4 . Pu(VI) was reduced to Pu(IV) with known excess of Fe(II). Uranium in the same solution was determined by reduction to U(IV) with Fe(II) in H 3 PO 4 medium. For the quantity of plutonium and uranium in the range of 3-5 mg per aliquot a precision of +-0.2% and +-0.4%, respectively, was obtained. (author)

Geochemical behaviour of uranium in sedimentary formations: insights from a natural analogue study - 16340

International Nuclear Information System (INIS)

Noseck, Ulrich; Brasser, Thomas; Havlova, Vaclava; Cervinka, Radek; Suksi, Juhani

2009-01-01

Groundwater data from the natural analogue site Ruprechtov have been evaluated with special emphasis on the uranium behaviour in the so-called uranium-rich clay/lignite horizon. In this horizon in-situ Eh-values in the range of -160 to -280 mV seem to be determined by the SO 4 2- /HS - couple. Under these conditions U(IV) is expected to be the preferential redox state in solution. However, on-site measurements in groundwater from the clay/lignite horizon show only a fraction of about 20 % occurring in the reduced state U(IV). Thermodynamic calculations reveal that the high CO 2 partial pressure in the clay/lignite horizon can stabilise hexavalent uranium, which explains the occurrence of U(VI). The calculations also indicate that the low uranium concentrations in the range between 0.2 and 2.1 μg/l are controlled by amorphous UO 2 and/or the U(IV) phosphate mineral ningyoite. This confirms the findings from previous work that the uranium (IV) mineral phases are long-term stable under the reducing conditions in the clay/lignite horizon without any signatures for uranium mobilisation. It supports the current knowledge of the geological development of the site and is also another important indication for the long-term stability of the sedimentary system itself, namely of the reducing geochemical conditions in the near-surface (30 m to 60 m deep) clay/lignite horizon. Further work with respect to the impact of changes in redox conditions on the uranium speciation is on the way. (authors)

Reaction of uranium (IV) with xenon difluoride by chemiluminescence, spectrophotometric, and spectrofluorimetric methods

Energy Technology Data Exchange (ETDEWEB)

Mamykin, A.V.; Kazakov, V.P.

1988-07-01

A study is made of the kinetics of the chemiluminescent reaction of oxidation of uranium (IV) by xenon difluoride in 1M HClO/sub 4/ U/sup 4 +/ + XeF/sub 2/ ..-->.. UO/sub 2//sup 2 +/ = h/eta/. The optical density D and the intensity of the photoluminescence of the solution I/sub PL/ were measured in parallel with recording of the luminescence intensity I/sub CL/. I/sub CL/ attains a maximum value some time after the beginning of the reaction, after which it decays exponentially. On the kinetic curves of the time dependence of D and I/sub PL/ an induction period is observed, the extent of which depends on concentrations of reagents and temperature of the solution. The maximum of I/sub CL/ coincides with the end of the induction period if the measurements are carried out under identical conditions. The rate of the reaction after the induction period is described by a first order equation in U/sup (IV)/. The rate constants of the reaction, obtained by chemiluminescence, spectrophotometric, and spectrofluorimetric methods, have close values 2.0 +- 0.4, 1.8 +- 0.3, and 2.1 +- 0.3 sec/sup /minus/1/ x 10/sup 2/, respectively. On the basis of the results obtained, we conclude that the stages of formation of UO/sub 2//sup 2 +/ and of chemiluminescence coincide, i.e., formation of the excited state (UD/sub 2//sup 2 +/) and of chemiluminescence coincide, i.e., formation of the excited state (UD/sub 2//sup 2 +/)* takes place during the reaction. It is proposed and experimentally verified that the reaction passes through an intermediate stage of formation of uranyl ion UO/sub 2//sup +/.

Microbial reduction of uranium(VI) by anaerobic microorganisms isolated from a former uranium mine

Energy Technology Data Exchange (ETDEWEB)

Gerber, Ulrike; Krawczyk-Baersch, Evelyn [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry; Arnold, Thuro [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology; Scheinost, Andreas C. [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Molecular Structures

2017-06-01

The former uranium mine Koenigstein (Germany) is currently in the process of controlled flooding by reason of remediation purposes. However, the flooding water still contains high concentrations of uranium and other heavy metals. For that reason the water has to be cleaned up by a conventional waste water treatment plant. The aim of this study was to investigate the interactions between anaerobic microorganisms and uranium for possible bioremediation approaches, which could be an great alternative for the intensive and expensive waste water treatment. EXAFS (extended X-ray absorption fine structure) and XANES (X-ray absorption near edge structure) measurements were performed and revealed a complete reduction of U(VI) to U(IV) only by adding 10 mM glycerol.

Microbial reduction of uranium(VI) by anaerobic microorganisms isolated from a former uranium mine

International Nuclear Information System (INIS)

Gerber, Ulrike; Krawczyk-Baersch, Evelyn; Arnold, Thuro; Scheinost, Andreas C.

2017-01-01

The former uranium mine Koenigstein (Germany) is currently in the process of controlled flooding by reason of remediation purposes. However, the flooding water still contains high concentrations of uranium and other heavy metals. For that reason the water has to be cleaned up by a conventional waste water treatment plant. The aim of this study was to investigate the interactions between anaerobic microorganisms and uranium for possible bioremediation approaches, which could be an great alternative for the intensive and expensive waste water treatment. EXAFS (extended X-ray absorption fine structure) and XANES (X-ray absorption near edge structure) measurements were performed and revealed a complete reduction of U(VI) to U(IV) only by adding 10 mM glycerol.

Uranium Elemental and Isotopic Constraints on Groundwater Flow Beneath the Nopal I Uranium Deposit, Pena Blanca, Mexico

International Nuclear Information System (INIS)

S.J. Goldstein; M.T. Murrell; A.M. Simmons

2005-01-01

The Nopal I uranium deposit in Chihuahua, Mexico, is an excellent analogue for evaluating the fate of spent fuel, associated actinides, and fission products over long time scales for the proposed Yucca Mountain high-level nuclear waste repository. In 2003, three groundwater wells were drilled directly adjacent to (PB-1) and 50 m on either side of the uranium deposit (PB-2 and PB-3) in order to evaluate uranium-series transport in three dimensions. After drilling, uranium concentrations were elevated in all of the three wells (0.1-18 ppm) due to drilling activities and subsequently decreased to ∼5-20% of initial values over the next several months. The 234 U/ 238 U activity ratios were similar for PB-1 and PB-2 (1.005 to 1.079) but distinct for PB-3 (1.36 to 1.83) over this time period, suggesting limited mixing between groundwater from these wells over these short time and length scales. Regional groundwater wells located up to several km from the deposit also have distinct uranium isotopic characteristics and constrain mixing over larger length and time scales. We model the decreasing uranium concentrations in the newly drilled wells with a simple one-dimensional advection-dispersion model, assuming uranium is introduced as a slug to each of the wells and transported as a conservative tracer. Using this model for our data, the relative uranium concentrations are dependent on both the longitudinal dispersion as well as the mean groundwater flow velocity. These parameters have been found to be correlated in both laboratory and field studies of groundwater velocity and dispersion (Klotz et al., 1980). Using typical relationships between velocity and dispersion for field and laboratory studies along with the relationship observed from our uranium data, both velocity (1-10 n/yr) and dispersion coefficient (1E-5 to 1E-2 cm 2 /s) can be derived from the modeling. As discussed above, these relatively small flow velocities and dispersivities agree with mixing

Uranium and thorium phosphate based matrices; syntheses, characterizations and lixiviation

International Nuclear Information System (INIS)

Dacheux, N.

1995-03-01

In the framework of the search for a ceramic material usable in the radioactive waste storage, uranium and thorium phosphates have been investigated. Their experimental synthesis conditions have been entirely reviewed, they lead to the preparation of four new compounds: U(UO 2 )(PO 4 ) 2 , U 2 O(PO 4 ) 2 , UC1PO 4 ,H 2 O, and Th 4 (PO 4 ) 4 , U 2 O 3 P 2 O 7 and Th 3 (PO 4 ) 4 . Characterization by several techniques (X-rays and neutron powder diffractions, UV-Visible and Infra-red spectroscopies, XPS,...) were performed. The ab initio structure determination of U(UO 2 )(PO 4 ) 2 has been achieved by X-rays and refined by neutron diffractions. Through its physico-chemical analysis, we found that this compound was a new mixed valence uranium phosphate in which U 4+ and UO 2 2+ ions are ordered in pairs along parallel chains according to a new type of arrangement. Reaction mechanism, starting from UC1PO 4 , 4H 2 O and based on redox processes of uranium in solid state was set up. From two main matrices U(UO 2 )(PO 4 ) 2 and Th 4 (PO 4 ) 4 P 2 O 7 , solid solutions were studied. They consist of replacement of U(IV) by Th(IV) and reversely. The leaching tests on pure, loaded and doped matrices were performed in terms of storage time, pH of solutions, and determined by the use of solids labelled with 230 U or by the measurement of uranyl concentration by Laser-Induced Time-Resolved Spectrofluorometry. Average concentration of uranium in the liquid phase is around 10 -4 M to 10 -6 M. Taking into account the very low solubilities of the studied phosphate ceramics, we estimated their chemical performances promising as an answer to the important nuclear waste problem, if we compare them to the glasses used at the present time. (author). 47 figs., 23 tabs., 6 appendixes

Uranium and thorium based phosphate matrix: synthesis, characterizations and lixiviation

International Nuclear Information System (INIS)

Dacheux, N.

1995-03-01

In the framework of the search for a ceramic material usable in the radioactive waste storage, uranium and thorium phosphates have been investigated. Their experimental synthesis conditions have been entirely reviewed, they lead to the preparation of four new compounds: U(UO 2 )(PO 4 ) 2 , U 2 O(PO 4 ) 2 , UCIPO 4 , 4H 2 O, and Th 4 (PO 4 ) 4 P 2 O 7 . Experimental evidenced are advanced for non existent compounds such as: U 3 (PO 4 ) 4 , U 2 O 3 P 2 O 7 and Th 3 (PO 4 ) 4 . Characterization by several techniques (X-rays and neutron powder diffractions, UV-Visible and Infra-red spectroscopies, XPS,...) were performed. The ab initio structure determination of U(UO 2 )(PO 4 ) 2 has been achieved by X-rays and refined by neutron diffractions. Through its physico-chemical analysis, we found that this compound was a new mixed valence uranium phosphate in which U 4+ and UO 2 2+ ions are ordered in pairs along parallel chains according to a new type of arrangement. Reaction mechanism, starting from UCIPO 4 , 4H 2 O and based on redox processes of uranium in solid state was set up. From two main matrices U(UO 2 )(PO 4 ) 2 and Th 4 (PO 4 ) 4 P 2 O 7 , solid solutions were studied. They consist of replacement of U(IV) by Th(IV) and reversely. The leaching tests on pure, loaded and doped matrices were performed in terms of storage time, pH of solutions, and determined by the use of solids labelled with 230 U or by the measurement of uranyl concentration by Laser-Induced Time-Resolved Spectro-fluorimetry. Average concentration of uranium in the liquid phase is around 10 -4 M to 10 -6 M. Taking into account the very low solubilities of the studied phosphate ceramics, we estimated their chemical performances promising as an answer to the important nuclear waste problem, if we compare them to the glasses used at the present time. (author)

Precision determination of uranium in uranium oxide by constant-current coulometry

International Nuclear Information System (INIS)

Xu Laili; Wang Chunhuan.

1990-01-01

A method of constant-current coulometric titration for determination of uranium in uranium oxide is described. This method involves preliminary reduction of U (VI) in H 2 SO 4 -H 3 PO 4 medium by Cr (II) as a reductant, followed by air oxidation of excess of Cr (II), addition of solid K 2 Cr 2 O 7 in quantity slightly more than that of the required for quantitative oxidation of U (IV) and final titration of excess of K 2 Cr 2 O 7 with the electrogenerated Fe (II). The endpoint is determined amperometrically. The effect of various factors on the sample treatment and reduction-oxidation processes has been examined. The precision of the method as indicated by the standard deviation of an individual observation is less than 0.01% for l gram uranium oxide

Uranium Immobilization in Wetland Soils

Science.gov (United States)

Jaffe, Peter R.; Koster van Groos, Paul G.; Li, Dien; Chang, Hyun-Shik; Seaman, John C.; Kaplan, Daniel I.; Peacock, Aaron D.; Scheckel, Kirk

2014-05-01

In wetlands, which are a major feature at the groundwater-surface water interface, plants deliver oxygen to the subsurface to keep root tissue aerobic. Some of this oxygen leaches into the rhizosphere where it will oxidize iron that typically precipitates on or near roots. Furthermore, plans provide carbon via root exudates and turnover, which in the presence of the iron oxides drives the activity of heterotrophic iron reducers in wetland soils. Oxidized iron is an important electron acceptor for many microbially-driven transformations, which can affect the fate and transport of several pollutants. It has been shown that heterotrophic iron reducing organisms, such as Geobacter sp., can reduce water soluble U(VI) to insoluble U(IV). The goal of this study was to determine if and how iron cycling in the wetland rhizosphere affects uranium dynamics. For this purpose, we operated a series of small-scale wetland mesocosms in a greenhouse to simulate the discharge of uranium-contaminated groundwater to surface waters. The mesocosms were operated with two different Fe(II) loading rates, two plant types, and unplanted controls. The mesocosms contained zones of root exclusion to differentiate between the direct presence and absence of roots in the planted mesocosms. The mesocosms were operated for several month to get fully established, after which a U(VI) solution was fed for 80 days. The mesocosms were then sacrificed and analyzed for solid-associated chemical species, microbiological characterization, micro-X-ray florescence (µ-XRF) mapping of Fe and U on the root surface, and U speciation via X-ray Absorption Near Edge Structure (XANES). Results showed that bacterial numbers including Geobacter sp., Fe(III), as well as total uranium, were highest on roots, followed by sediments near roots, and lowest in zones without much root influence. Results from the µ-XRF mapping on root surfaces indicated a strong spatial correlation between Fe and U. This correlation was

Impact of uranium-233/thorium cycle on advanced accountability concepts and fabrication facilities. Addendum 2 to application of advanced accountability concepts in mixed oxide fabrication

International Nuclear Information System (INIS)

Bastin, J.J.; Jump, M.J.; Lange, R.A.; Crandall, C.C.

1977-11-01

The Phase I study of the application of advanced accountability methods (DYMAC) in a uranium/plutonium mixed oxide facility was extended to cover the possible fabrication of uranium-233/thorium fuels. Revisions to Phase II of the DYMAC plan which would be necessitated by such a process are specified. These revisions include shielding requirements, measurement systems, licensing conditions, and safeguards considerations. The impact of the uranium/thorium cycle on a large-scale fuel fabrication facility was also reviewed; it was concluded that the essentially higher radioactivity of uranium/thorium feeds would lead to increased difficulties which tend to preclude early commercial application of the process. An amended schedule for Phase II is included

Oxidation state analyses of uranium with emphasis on chemical speciation in geological media

International Nuclear Information System (INIS)

Ervanne, H.

2004-01-01

This thesis focuses on chemical methods suitable for the determination of uranium redox species in geological materials. Nd-coprecipitation method was studied for the determination of uranium oxidation states in ground waters. This method is ideally suited for the separation of uranium oxidation states in the field, which means that problems associated with the instability of U(IV) during transport are avoided. An alternative method, such as ion exchange, is recommended for the analysis of high saline and calcium- and iron-rich ground waters. U(IV)/Utot was 2.8-7.2% in ground waters in oxidizing conditions and 60-93% in anoxic conditions. From thermodynamic model calculations applied to results from anoxic ground waters it was concluded that uranium can act as redox buffer in granitic ground waters. An ion exchange method was developed for the analysis of uranium oxidation states in different solid materials of geological origin. These included uranium minerals, uraniumbearing minerals, fracture coatings and bulk rock. U(IV)/Utot was 50-70% in uraninites, 5.8-8.7% in secondary uranium minerals, 15-49% in different fracture coatings and 64- 77% in samples from deep bedrock. In the uranium-bearing minerals, U(IV)/Utot was 33-43% (allanites), 5.9% (fergusonite) and 93% (monazite). Although the ion exchange method gave reliable results, there is a risk for the conversion of uranium oxidation states during analysis of heterogeneous samples due to the redox reactions that take place in the presence of some iron compounds. This risk was investigated in a study of several common iron-bearing minerals. The risk for conversion of uranium oxidation states can be screened by sample selection and minimized with use of a redox buffer compound such as polyacrylic acid (PAA). In studies of several carboxylic acids, PAA was found to be the most suitable for extending the application of the method. The stability of uranium oxidation states during analysis and the selectivity

Some reactions of hydrotris(3,5-dimethylpyrazolyl)-borato trichloroactinides(IV), MCl/sub 3/(HBL/sub 3/). THF (M=Th/sup IV/, U/sup IV/; L=3,5-dimethylpyrazolyl, THF=tetrahydrofuran)

Energy Technology Data Exchange (ETDEWEB)

Marcalo, J; Marques, N; Pires de Matos, A; Bagnall, K W

1986-08-01

The thorium(IV) and uranium(IV) compounds MCl/sub 2/(Cp)(HBL/sub 3/) (Cp=eta/sup 5/-C/sub 5/H/sub 5/), MCl/sub 2/(N(SiMe/sub 3/)/sub 2/)(HBL/sub 3/) and M(NPh/sub 2/)/sub 3/(HBL/sub 3/) have been prepared from MCl/sub 3/(HBL/sub 3/).THF. IR, near-IR-visible, /sup 1/H NMR and /sup 11/B NMR spectra are reported for these compounds.

Comparison of open cycles of uranium and mixed oxides of thorium-uranium using advanced reactors; Comparação de ciclos abertos de urânio e óxidos mistos de tório-urânio utilizando reatores avançados

Energy Technology Data Exchange (ETDEWEB)

Gonçalves, Letícia C.; Maiorino, José R., E-mail: goncalves.leticiac@gmail.com [Universidade Federal do ABC (UFABC), Santo André, SP (Brazil). Centro de Engenharia, Modelagem e Ciências Sociais Aplicadas

2017-07-01

A comparative study of the mass balance and production costs of uranium oxide fuels was carried out for an AP1000 reactor and thorium-uranium mixed oxide in a reactor proposal using thorium called AP-Th1000. Assuming the input mass values for a fuel load the average enrichment for both reactors as well as their feed mass was determined. With these parameters, the costs were calculated in each fuel preparation process, assuming the prices provided by the World Nuclear Association. The total fuel costs for the two reactors were quantitatively compared with 18-month open cycle. Considering enrichment of 20% for the open cycle of mixed U-Th oxide fuel, the total uranium consumption of this option was 50% higher and the cost due to the enrichment was 70% higher. The results show that the use of U-Th mixed oxide fuels can be advantageous considering sustainability issues. In this case other parameters and conditions should be investigated, especially those related to fuel recycling, spent fuel storage and reduction of the amount of transuranic radioactive waste.

Chemical states of fission products in irradiated uranium-plutonium mixed oxide fuel

International Nuclear Information System (INIS)

Kurosaki, Ken; Uno, Masayoshi; Yamanaka, Shinsuke

1999-01-01

The chemical states of fission products (FPs) in irradiated uranium-plutonium mixed oxide (MOX) fuel for the light water reactor (LWR) were estimated by thermodynamic equilibrium calculations on system of fuel and FPs by using ChemSage program. A stoichiometric MOX containing 6.1 wt. percent PuO 2 was taken as a loading fuel. The variation of chemical states of FPs was calculated as a function of oxygen potential. Some pieces of information obtained by the calculation were compared with the results of the post-irradiation examination (PIE) of UO 2 fuel. It was confirmed that the multicomponent and multiphase thermodynamic equilibrium calculation between fuel and FPs system was an effective tool for understanding the behavior of FPs in fuel. (author)

Formation conditions for regenerated uranium blacks in uranium-molybdenum deposits

International Nuclear Information System (INIS)

Skvortsova, K.V.; Sychev, I.V.; Modnikov, I.S.; Zhil'tsova, I.G.

1980-01-01

Formation conditions of regenerated uranium blacks in the zone of incomplete oxidation and cementation of uranium-molybdenum deposit have been studied. Mixed and regenerated blacks were differed from residual ones by the method of determining excess quantity of lead isotope (Pb 206 ) in ores. Determined were the most favourable conditions for formation of regenerated uranium blacks: sheets of brittle and permeable volcanic rocks characterized by heterogeneous structure of a section, by considerable development of gentle interlayer strippings and zones of hydrothermal alteration; predominance of reduction conditions in a media over oxidation ones under limited oxygen access and other oxidating agents; the composition of hypogenic ores characterized by optimum correlations of uranium minerals, sulfides and carbonates affecting violations of pH in oxidating solutions in the range of 5-6; the initial composition of ground water resulting from climatic conditions of the region and the composition of ore-bearing strata and others. Conditions unfavourable for the formation of regenerated uranium blacks are shown

Uranium resource assessments

International Nuclear Information System (INIS)

1981-01-01

The objective of this investigation is to examine what is generally known about uranium resources, what is subject to conjecture, how well do the explorers themselves understand the occurrence of uranium, and who are the various participants in the exploration process. From this we hope to reach a better understanding of the quality of uranium resource estimates as well as the nature of the exploration process. The underlying questions will remain unanswered. But given an inability to estimate precisely our uranium resources, how much do we really need to know. To answer this latter question, the various Department of Energy needs for uranium resource estimates are examined. This allows consideration of whether or not given the absence of more complete long-term supply data and the associated problems of uranium deliverability for the electric utility industry, we are now threatened with nuclear power plants eventually standing idle due to an unanticipated lack of fuel for their reactors. Obviously this is of some consequence to the government and energy consuming public. The report is organized into four parts. Section I evaluates the uranium resource data base and the various methodologies of resource assessment. Part II describes the manner in which a private company goes about exploring for uranium and the nature of its internal need for resource information. Part III examines the structure of the industry for the purpose of determining the character of the industry with respect to resource development. Part IV arrives at conclusions about the emerging pattern of industrial behavior with respect to uranium supply and the implications this has for coping with national energy issues

Uranium recovery from mine water

International Nuclear Information System (INIS)

Sarkar, K.M.

1984-01-01

In many plant trials it has been proven that very small amounts (10 to 20 ppm) of uranium dissolved in mine water can be effectively recovered by the use of ion exchange resins and this uranium recovery has many advantages. In this paper an economic analysis at different levels of uranium contamination and at different market prices of uranium are described. For this study an operating mine-mill complex with a sulphuric acid leach circuit, followed by solvent extraction (SX) process, is considered, where contaminated mine water is available in excess of process requirements. It is further assumed that the sulphuric acid eluant containing uranium would be mixed with the mill pregnant liquor stream that proceeds to the SX plant for final uranium recovery

Stabilization of mixed carbides of uranium-plutonium by zirconium. Part 1.: uranium carbide with small additions of zirconium; Etude de la stabilisation des carbures mixtes d'uranium et de plutonium par addition de zirconium. 1. partie: etude des carbures d'uranium avec de faibles additions de zirconium

Energy Technology Data Exchange (ETDEWEB)

Bocker, S [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1969-07-01

Cast carbide samples, being of a high density and purity, are preferable for research purposes, to samples produced by powder metallurgy methods. Samples of uranium carbide with small additions of zirconium (1 to 5 per cent) were cast, as rods, in an arc furnace. A single phase carbide with interesting qualities was produced. As cast, a dendrite structure is observed, which does not disappear, after a treatment at 1900 deg. C during 110 hours. In comparison with uranium monocarbide the compatibility with stainless steel is much improved. The specific heat (between room temperature and 2500 deg. C) is similar to the specific heat of uranium monocarbide. A study of these mixed carbides, but having a part of the uranium replaced by plutonium is under way. (author) [French] Les echantillons de monocarbures obtenus par coulee sont tres interessants pour les recherches experimentales a cause de leur grande purete, de leur densite tres elevee et de la facilite d'obtention des lingots de forme et dimensions variees. On a prepare et coule dans un four a arc des echantillons de carbures d'uranium avec de faibles additions de zirconium (1 a 5 at. pour cent). On obtient ainsi des carbures monophases presentant de meilleures proprietes que le monocarbure d'uranium. A l'etat brut de coulee on observe une structure dendritique qui n'est pas detruite par un traitement thermique de 110 heures a 1900 deg. C. La compatibilite avec l'acier inoxydable 316 (a 925 deg. C pendant 500 heures) est nettement amelioree par rapport a UC. La chaleur specifique (entre la temperature ordinaire et 2500 deg. C) et la densite sont tres peu differentes de celles du monocarbure d'uranium. Une etude concernant les composes U-Pu-Zr-C est actuellement en cours. (auteur)

U(IV) fluorescence spectroscopy. A new speciation tool

Energy Technology Data Exchange (ETDEWEB)

Lehmann, Susanne; Brendler, Vinzenz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes; Steudtner, Robin [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology

2017-06-01

We combined absorption and fluorescence spectroscopy to study the speciation of U(IV) in solution in concentrations down to 10{sup -6} M uranium. With our time-resolved laser-induced fluorescence setup we could determine the fluorescence decay time of U(IV) in perchloric as well as in chloric acid with 2.6 ± 0.3 ns at room temperature and 148.4 ± 6.5 ns at liquid nitrogen temperature. For the U(IV) sulfate system, we observed a bathochromic shift and a peak shape modification in the fluorescence spectra with increasing sulfate concentration in solution. Thus, the potential of U(IV) fluorescence for speciation analysis could be proven.

Melting temperature of uranium - plutonium mixed oxide fuel

Energy Technology Data Exchange (ETDEWEB)

Ishii, Tetsuya; Hirosawa, Takashi [Power Reactor and Nuclear Fuel Development Corp., Oarai, Ibaraki (Japan). Oarai Engineering Center

1997-08-01

Fuel melting temperature is one of the major thermodynamical properties that is used for determining the design criteria on fuel temperature during irradiation in FBR. In general, it is necessary to evaluate the correlation of fuel melting temperature to confirm that the fuel temperature must be kept below the fuel melting temperature during irradiation at any conditions. The correlations of the melting temperature of uranium-plutonium mixed oxide (MOX) fuel, typical FBR fuel, used to be estimated and formulized based on the measured values reported in 1960`s and has been applied to the design. At present, some experiments have been accumulated with improved experimental techniques. And it reveals that the recent measured melting temperatures does not agree well to the data reported in 1960`s and that some of the 1960`s data should be modified by taking into account of the recent measurements. In this study, the experience of melting temperature up to now are summarized and evaluated in order to make the fuel pin design more reliable. The effect of plutonium content, oxygen to metal ratio and burnup on MOX fuel melting was examined based on the recent data under the UO{sub 2} - PuO{sub 2} - PuO{sub 1.61} ideal solution model, and then formulized. (J.P.N.)

Melting temperature of uranium - plutonium mixed oxide fuel

International Nuclear Information System (INIS)

Ishii, Tetsuya; Hirosawa, Takashi

1997-08-01

Fuel melting temperature is one of the major thermodynamical properties that is used for determining the design criteria on fuel temperature during irradiation in FBR. In general, it is necessary to evaluate the correlation of fuel melting temperature to confirm that the fuel temperature must be kept below the fuel melting temperature during irradiation at any conditions. The correlations of the melting temperature of uranium-plutonium mixed oxide (MOX) fuel, typical FBR fuel, used to be estimated and formulized based on the measured values reported in 1960's and has been applied to the design. At present, some experiments have been accumulated with improved experimental techniques. And it reveals that the recent measured melting temperatures does not agree well to the data reported in 1960's and that some of the 1960's data should be modified by taking into account of the recent measurements. In this study, the experience of melting temperature up to now are summarized and evaluated in order to make the fuel pin design more reliable. The effect of plutonium content, oxygen to metal ratio and burnup on MOX fuel melting was examined based on the recent data under the UO 2 - PuO 2 - PuO 1.61 ideal solution model, and then formulized. (J.P.N.)

Microbial uptake of uranium, cesium, and radium

Energy Technology Data Exchange (ETDEWEB)

Strandberg, G.W.; Shumate, S.E. II; Parrott, J.R. Jr.; McWhirter, D.A.

1980-01-01

The ability of diverse microbial species to concentrate uranium, cesium, and radium was examined. Saccharomyces cerevisiae, Pseudomonas aeruginosa, and a mixed culture of denitrifying bacteria accumulated uranium to 10 to 15% of the dry cell weight. Only a fraction of the cells in a given population had visible uranium deposits in electron micrographs. While metabolism was not required for uranium uptake, mechanistic differences in the metal uptake process were indicated. Uranium accumulated slowly (hours) on the surface of S. cerevisiae and was subject to environmental factors (i.e., temperature, pH, interfering cations and anions). In contrast, P. aeruginosa and the mixed culture of denitrifying bacteria accumulated uranium rapidly (minutes) as dense, apparently random, intracellular deposits. This very rapid accumulation has prevented us from determining whether the uptake rate during the transient between the initial and equilibrium distribution of uranium is affected by environmental conditions. However, the final equilibrium distributions are not affected by those conditions which affect uptake by S. cerevisiae. Cesium and radium were concentrated to a considerably lesser extent than uranium by the several microbial species tested. The potential utility of microorganisms for the removal and concentration of these metals from nuclear processing wastes and several bioreactor designs for contacting microorganisms with contaminated waste streams will be discussed.

Complexes of uranium (IV) and thorium (IV) with α-picolinic acid, nicotinic acid, anthranilic acid and N-phenylanthranilic acid

International Nuclear Information System (INIS)

Singh, M.; Singh, R.

1979-01-01

Stable U(IV) and Th(IV) complexes with the title ligands have been synthesised from U(OAc) 4 , and Th(OAc) 4 . Magnetic susceptibilities, IR and reflectance spectra of U(IV) and IR spectra of Th(IV) complexes have been studied which indicate eight coordination for U(IV) in these chelates. (auth.)

The measurement test of uranium in a uranium-contaminated waste by passive gamma-rays measurement method

CERN Document Server

Sukegawa, Y; Ohki, K; Suzuki, S; Yoshida, M

2002-01-01

This report is completed about the measurement test and the proofreading of passive gamma - rays measurement method for Non - destructive assay of uranium in a uranium-contaminated waste. The following are the results of the test. 1) The estimation of the amount of uranium by ionization survey meter is difficult for low intensity of gamma-rays emitted from uranium under about 50g. 2) The estimation of the amount of uranium in the waste by NaI detector is possible in case of only uranium, but the estimation from mixed spectrums with transmission source (60-cobalt) is difficult to confirm target peaks. 3) If daughter nuclides of uranium and thorium chain of uranium ore exist, measurement by NaI detector is affected by gamma-rays from the daughter nuclides seriously-As a result, the estimation of the amount of uranium is difficult. 4) The measurement of uranium in a uranium-contaminated waste by germanium detector is possible to estimate of uranium and other nuclides. 5) As to estimation of the amount of uranium...

Method to manufacture a nuclear fuel from uranium-plutonium monocarbide or uranium-plutonium mononitride

International Nuclear Information System (INIS)

Krauth, A.; Mueller, N.

1977-01-01

Pure uranium carbide or nitride is converted with plutonium oxide and carbon (all in powder form) to uranium-plutonium monocarbide or mononitride by cold pressing and sintering at about 1600 0 C. Pure uranium carbide or uranium nitride powder is firstly prepared without extensive safety measures. The pure uranium carbide or nitride powder can also be inactivated by using chemical substances (e.g. stearic acid) and be handled in air. The sinterable uranium carbide or nitride powder (or also granulate) is then introduced into the plutonium line and mixed with a nonstoichiometrically adjusted, prereacted mixture of plutonium oxide and carbon, pressed to pellets and reaction sintered. The surface of the uranium-plutonium carbide (higher metal content) can be nitrated towards the end of the sinter process in a stream of nitrogen. The protective layer stabilizes the carbide against the water and oxygen content in air. (IHOE) [de

Deployable nuclear fleet based on available quantities of uranium and reactor types – the case of fast reactors started up with enriched uranium

Directory of Open Access Journals (Sweden)

Baschwitz Anne

2016-01-01

Full Text Available International organizations regularly produce global energy demand scenarios. To account for the increasing population and GDP trends, as well as to encompass evolving energy uses while satisfying constraints on greenhouse gas emissions, long-term installed nuclear power capacity scenarios tend to be more ambitious, even after the Fukushima accident. Thus, the amounts of uranium or plutonium needed to deploy such capacities could be limiting factors. This study first considers light-water reactors (LWR, GEN III using enriched uranium, like most of the current reactor technologies. It then examines the contribution of future fast reactors (FR, GEN IV operating with an initial fissile load and then using depleted uranium and recycling their own plutonium. However, as plutonium is only available in limited quantity since it is only produced in nuclear reactors, the possibility of starting up these Generation IV reactors with a fissile load of enriched uranium is also explored. In one of our previous studies, the uranium consumption of a third-generation reactor like an EPR™ was compared with that of a fast reactor started up with enriched uranium (U5-FR. For a reactor lifespan of 60 years, the U5-FR consumes three times less uranium than the EPR and represents a 60% reduction in terms of separative work units (SWU, though its requirements are concentrated over the first few years of operation. The purpose of this study is to investigate the relevance of U5-FRs in a nuclear fleet deployment configuration. Considering several power demand scenarios and assuming different finite quantities of available natural uranium, this paper examines what types of reactors must be deployed to meet the demand. The deployment of light-water reactors only is not sustainable in the long run. Generation IV reactors are therefore essential. Yet when started up with plutonium, the number of reactors that can be deployed is also limited. In a fleet deployment

A spectroscopic study of uranium(VI) interaction with magnetite

International Nuclear Information System (INIS)

El Aamrani, S.; Gimenez, J.; Rovira, M.; Seco, F.; Grive, M.; Bruno, J.; Duro, L.; Pablo, J. de

2007-01-01

The uranium sorbed onto commercial magnetite has been characterized by using two different spectroscopic techniques such as X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS). Magnetite samples have been put in contact with uranium(VI) solutions in conditions in which a high uranium uptake is expected. After several days, the magnetite surface has been analysed by XPS and EXAFS. The XPS results obtained are not conclusive regarding the uranium oxidation state in the magnetite surface. On the other hand, the results obtained with the EXAFS technique show that the uranium-magnetite sample spectrum has characteristics from both the UO 2 and schoepite spectra, e.g. a relatively high coordination number of equatorial oxygens and two axial oxygens, respectively. These results would indicate that the uranium sorbed onto magnetite would be a mixture of uranium(IV) and uranium(VI)

In situ spectroscopy and spectroelectrochemistry of uranium in high-temperature alkali chloride molten salts.

Science.gov (United States)

Polovov, Ilya B; Volkovich, Vladimir A; Charnock, John M; Kralj, Brett; Lewin, Robert G; Kinoshita, Hajime; May, Iain; Sharrad, Clint A

2008-09-01

Soluble uranium chloride species, in the oxidation states of III+, IV+, V+, and VI+, have been chemically generated in high-temperature alkali chloride melts. These reactions were monitored by in situ electronic absorption spectroscopy. In situ X-ray absorption spectroscopy of uranium(VI) in a molten LiCl-KCl eutectic was used to determine the immediate coordination environment about the uranium. The dominant species in the melt was [UO 2Cl 4] (2-). Further analysis of the extended X-ray absorption fine structure data and Raman spectroscopy of the melts quenched back to room temperature indicated the possibility of ordering beyond the first coordination sphere of [UO 2Cl 4] (2-). The electrolytic generation of uranium(III) in a molten LiCl-KCl eutectic was also investigated. Anodic dissolution of uranium metal was found to be more efficient at producing uranium(III) in high-temperature melts than the cathodic reduction of uranium(IV). These high-temperature electrolytic processes were studied by in situ electronic absorption spectroelectrochemistry, and we have also developed in situ X-ray absorption spectroelectrochemistry techniques to probe both the uranium oxidation state and the uranium coordination environment in these melts.

Ionic flotation of uranium contained in industrial phosphoric acid

International Nuclear Information System (INIS)

Jdid; Blazy; Bessiere

1983-01-01

A new process for uranium recovery from industrial phosphoric acid at 30% of P 2 O 5 is applied by the ionic flotation process. Research is carried out on determination of the nature of ionic species of U in H 3 PO 4 5.5 M and the behavior of reagents from CECA Co. in very acid media. Reagents able to form complexes directly with uranium and stable in phosphoric acid selected are: potassium ethylene diamine tetra (methylene phosphonate) (INIPOL AD32) and sodium dialkyldiphosphonate (34S). Uranium IV, obtained by reduction of uranium VI with iron powder, is precipitated by these reagents. Flotation of the precipitate obtained with INIPOL AD 32 is realized by addition of hexylamino bis (methylene phosphonic acid). A recovery of 80 wt% is obtained. Flotation of the coprecipitate 34S-U(IV) is obtained without any other additions because 34S is a surfactant. Metal recovery is better than 90% and the coprecipitate contains more than 10% U. The process is fast precipitation 10 minutes and flotation 5 minutes and is efficient even at 60 0 C [fr

Automated uranium titration system

International Nuclear Information System (INIS)

Takahashi, M.; Kato, Y.

1983-01-01

An automated titration system based on the Davies-Gray method has been developed for accurate determination of uranium. The system consists of a potentiometric titrator with precise burettes, a sample changer, an electronic balance and a desk-top computer with a printer. Fifty-five titration vessels are loaded in the sample changer. The first three contain the standard solution for standardizing potassium dichromate titrant, and the next two and the last two contain the control samples for data quality assurance. The other forty-eight measurements are carried out for sixteen unknown samples. Sample solution containing about 100 mg uranium is taken in a titration vessel. At the pretreatment position, uranium (VI) is reduced to uranium (IV) by iron (II). After the valency adjustment, the vessel is transferred to the titration position. The rate of titrant addition is automatically controlled to be slower near the end-point. The last figure (0.01 mL) of the equivalent titrant volume for uranium is calculated from the potential change. The results obtained with this system on 100 mg uranium gave a precision of 0.2% (RSD,n=3) and an accuracy of better than 0.1%. Fifty-five titrations are accomplished in 10 hours. (author)

Uranium Elemental and Isotopic Constraints on Groundwater Flow Beneath the Nopal I Uranium Deposit, Pena Blanca, Mexico

Energy Technology Data Exchange (ETDEWEB)

S.J. Goldstein; M.T. Murrell; A.M. Simmons

2005-07-11

The Nopal I uranium deposit in Chihuahua, Mexico, is an excellent analogue for evaluating the fate of spent fuel, associated actinides, and fission products over long time scales for the proposed Yucca Mountain high-level nuclear waste repository. In 2003, three groundwater wells were drilled directly adjacent to (PB-1) and 50 m on either side of the uranium deposit (PB-2 and PB-3) in order to evaluate uranium-series transport in three dimensions. After drilling, uranium concentrations were elevated in all of the three wells (0.1-18 ppm) due to drilling activities and subsequently decreased to {approx}5-20% of initial values over the next several months. The {sup 234}U/{sup 238}U activity ratios were similar for PB-1 and PB-2 (1.005 to 1.079) but distinct for PB-3 (1.36 to 1.83) over this time period, suggesting limited mixing between groundwater from these wells over these short time and length scales. Regional groundwater wells located up to several km from the deposit also have distinct uranium isotopic characteristics and constrain mixing over larger length and time scales. We model the decreasing uranium concentrations in the newly drilled wells with a simple one-dimensional advection-dispersion model, assuming uranium is introduced as a slug to each of the wells and transported as a conservative tracer. Using this model for our data, the relative uranium concentrations are dependent on both the longitudinal dispersion as well as the mean groundwater flow velocity. These parameters have been found to be correlated in both laboratory and field studies of groundwater velocity and dispersion (Klotz et al., 1980). Using typical relationships between velocity and dispersion for field and laboratory studies along with the relationship observed from our uranium data, both velocity (1-10 n/yr) and dispersion coefficient (1E-5 to 1E-2 cm{sup 2}/s) can be derived from the modeling. As discussed above, these relatively small flow velocities and dispersivities agree with

Application of ion exchange to isotope separation. 2. Isotope separation of uranium

Energy Technology Data Exchange (ETDEWEB)

Okamoto, Makoto; Fujii, Yasuhiko; Aida, Masao; Nomura, Masao; Aoyama, Taku

1985-10-01

Research work on the uranium isotope separation by ion exchange chromatography done by the ahthors was reviewed and summarized in the present paper. Specifically described are the determination of separation coefficients of uranium isotopes in various chemical systems involving uranium ions and complexes. The chemical systems are classifield into three main categories; (1) uranyl, U (VI), complex formation system, (2) uranous, U (IV), complex formation system and (3) U (IV) - U (VI) redox system. The redox system showed the largest separation coefficient of approx. 7 x 10/sup -4/, while the uranyl and uranous complex systems showed the separation coefficients of -- 2 x 10/sup -4/ and approx. 6 x 10/sup -5/, respectively.

Recycling of reprocessed uranium

International Nuclear Information System (INIS)

Randl, R.P.

1987-01-01

Since nuclear power was first exploited in the Federal Republic of Germany, the philosophy underlying the strategy of the nuclear fuel cycle has been to make optimum use of the resource potential of recovered uranium and plutonium within a closed fuel cycle. Apart from the weighty argument of reprocessing being an important step in the treatment and disposal of radioactive wastes, permitting their optimum ecological conditioning after the reprocessing step and subsequent storage underground, another argument that, no doubt, carried weight was the possibility of reducing the demand of power plants for natural uranium. In recent years, strategies of recycling have emerged for reprocessed uranium. If that energy potential, too, is to be exploited by thermal recycling, it is appropriate to choose a slightly different method of recycling from the one for plutonium. While the first generation of reprocessed uranium fuel recycled in the reactor cuts down natural uranium requirement by some 15%, the recycling of a second generation of reprocessed, once more enriched uranium fuel helps only to save a further three per cent of natural uranium. Uranium of the second generation already carries uranium-232 isotope, causing production disturbances, and uranium-236 isotope, causing disturbances of the neutron balance in the reactor, in such amounts as to make further fabrication of uranium fuel elements inexpedient, even after mixing with natural uranium feed. (orig./UA) [de

Plutonium-uranium mixed oxide characterization by coupling micro-X-ray diffraction and absorption investigations

Science.gov (United States)

Degueldre, C.; Martin, M.; Kuri, G.; Grolimund, D.; Borca, C.

2011-09-01

Plutonium-uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The potential differences of metal redox state and microstructural developments of the matrix before and after irradiation are commonly analysed by electron probe microanalysis. In this work the structure and next-neighbor atomic environments of Pu and U oxide features within unirradiated homogeneous MOX and irradiated (60 MW d kg -1) MOX samples was analysed by micro-X-ray fluorescence (μ-XRF), micro-X-ray diffraction (μ-XRD) and micro-X-ray absorption fine structure (μ-XAFS) spectroscopy. The grain properties, chemical bonding, valences and stoichiometry of Pu and U are determined from the experimental data gained for the unirradiated as well as for irradiated fuel material examined in the center of the fuel as well as in its peripheral zone (rim). The formation of sub-grains is observed as well as their development from the center to the rim (polygonization). In the irradiated sample Pu remains tetravalent (>95%) and no (oxidation in the rim zone. Any slight potential plutonium oxidation is buffered by the uranium dioxide matrix while locally fuel cladding interaction could also affect the redox of the fuel.

Chemical aspects of rubidium uranium sulphate for its use as a chemical standard for uranium

International Nuclear Information System (INIS)

Singh Mudher, K.D.; Khandekar, R.R.; Krishnan, K.; Jayadevan, N.C.; Sood, D.D.

1989-01-01

Rb 2 U(SO 4 ) 3 , a double sulphate of rubidium and uranium(IV) has been prepared and investigated for its use as a chemical standard for uranium. The compound can be easily prepared and crystallised in a pure form. The results of physico-chemical characterisation on preparation of 5-10 g. lots are described in this report. These studies suggest that the compound is anhydrous, stoichiometric, stable to atmospheric effects and easily soluble in acids and thus satisfies most of the criteria for a primary standard. (author). 13 refs., 4 figs., 6 tabs

Mixed core management: Use of 93% and 72% enriched uranium in the BR2 reactor

International Nuclear Information System (INIS)

Ponsard, B.

2000-01-01

The BR2 reactor, put into operation in 1963 and refurbished from July 1995 till April 1997, is a 100 MW high-flux Materials Testing Reactor, using 93% 235 U enriched uranium as standard fuel, light water as coolant and beryllium as moderator. The present operating regime consists of five irradiation cycles per year at an operating power between 50 and 70 MW; each cycle is characterized by 21 days operation. In the framework of a 'qualification programme', six 72% 235 U fuel elements fabricated with uranium recovered from the reprocessing of BR2 spent fuel at UKAEA-Dounreay have been successfully irradiated in the period 1994-1995 reaching a maximum mean burnup of 48% without the release of fission products. Since 1998, this type of fuel element is irradiated routinely together with standard 93% 235 U fuel elements in order to optimize the utilization of the available HEU inventory. The purpose of this paper is to present the strategy developed in order to optimize the mixed core management of the BR2 reactor. (author)

Extraction behavior of uranium(VI) with polyurethane foam

International Nuclear Information System (INIS)

Tingchia Huang; Donghwang Chen; Muchang Shieh; Chingtsven Huang

1992-01-01

The extraction of uranium(VI) from aqueous solution with polyether-based polyurethane (PU) foam was studied. The effects of the kinds and concentrations of nitrate salts, uranium(VI) concentration, temperature, nitric acid concentration, pH, the content of poly(ethylene oxide) in the polyurethane foam, and the ratio of PU foam weight and solution volume on the extraction of uranium(VI) were investigated. The interferences of fluoride and carbonate ions on the extraction of uranium(VI) were also examined, and methods to overcome both interferences were suggested. It was found that no uranium was extracted in the absence of a nitrate salting-out agent, and the extraction behaviors of uranium(IV) with polyurethane foam could be explained in terms of an etherlike solvent extraction mechanism. In addition, the percentage extraction of a multiple stage was also estimated theoretically

EPR of uranium ions

International Nuclear Information System (INIS)

Ursu, I.; Lupei, V.

1984-02-01

A review of the electron paramagnetic resonance data on the uranium ions is given. After a general account of the electronic structure of the uranium free atoms and ions, the influence of the external fields (magnetic field, crystal fields) is discussed. The main information obtained from EPR studies on the uranium ions in crystals are emphasized: identification of the valence and of the ground electronic state, determination of the structure of the centers, crystal field effects, role of the intermediate coupling and of the J-mixing, role of the covalency, determination of the nuclear spin, maqnetic dipole moment and electric quadrupole moment of the odd isotopes of uranium. These data emphasize the fact that the actinide group has its own identity and this is accutely manifested at the beginning of the 5fsup(n) series encompassed by the uranium ions. (authors)

A gravimetric method for the determination of oxygen in uranium oxides and ternary uranium oxides by addition of alkaline earth compounds

International Nuclear Information System (INIS)

Fujino, Takeo; Tagawa, Hiroaki; Adachi, Takeo; Hashitani, Hiroshi

1978-01-01

A simple gravimetric determination of oxygen in uranium oxides and ternary uranium oxides is described. In alkaline earth uranates which are formed by heating in air at 800-1100 0 C, uranium is in the hexavalent state over certain continuous ranges of alkaline earth-to-uranium ratios. Thus, if an alkaline earth uranate or a compound containing an alkaline earth element, e.g. MgO, is mixed with the oxide sample and heated in air under suitable conditions, oxygen can be determined from the weight change before and after the reaction. The standard deviation of the O:U ratio for a UOsub(2+x) test sample is +-0.0008-0.001, if a correction is applied for atmospheric moisture absorbed during mixing. (Auth.)

Complexation of the An(IV) by NTA; Complexation des An(IV) par le NTA

Energy Technology Data Exchange (ETDEWEB)

Bonin, L. [Paris-11 Univ., 91 - Orsay (France)]|[CEA Valrho, Lab. de Chimie des Actinides (LCA), 30 - Marcoule (France)

2006-07-01

In the framework of the Nuclear and Environmental Toxicology program, developed in France, it has been decided to take again the studies concerning the actinides decorporation. A similar study of the neptunium complexation by the citrate ions has been carried out on the complexation of Np(IV) with the nitrilotriacetic acid (NTA). The NTA can be considered as a model molecule of the de-corporating molecules (amino-carboxy- ligand). The results of the spectrophotometric measurements being encouraging, the behaviour of several actinides at the same oxidation state (+IV) (Th(IV), U(IV), Np(IV), and Pu(IV)) has been determined. The experimental results are presented. In order to determine the structure of the complexes of stoichiometry 1:2 An(IV)-(NTA){sub 2} in solution, quantic chemistry calculations and EXAFS measurements have been carried out in parallel. These studies confirm the presence of An(IV)-nitrogen bonds whose length decreases from thorium to plutonium and indicate the presence of a water molecule bound to the thorium and the uranium (coordination number 8 for Np/Pu, 9 for Th/U). The evolution of the complexation constants determined in this study in terms of 1/r (r ionic radius of the cation taking into account its coordination number 8 or 9) confirms the change of the coordination number between Th/U and Np/Pu. (O.M.)

Ligand influences on properties of uranium coordination complexes. Structure, reactivity, and spectroscopy

International Nuclear Information System (INIS)

Kosog, Boris

2012-01-01

In this thesis several different aspects of uranium chemistry are presented. It was shown that terminal uranium(V) oxo and imido complexes [(( R ArO) 3 tacn)U V (O)] and [(( R ArO) 3 tacn)U V (NSiMe 3 )] (R = t Bu, Ad) can be oxidized by silver(I) hexafluoro-antimonate to the uranium(VI) oxo and imido complexes [(( R ArO) 3 tacn)U VI (O)]SbF 6 and [(( R ArO) 3 tacn)U VI (NSiMe 3 )]SbF 6 . While for the t Bu-derivative of the oxo complex an equatorial coordination is observed due to stabilization by the inverse trans-influence, normal axial coordination is observed for the Ad-derivative and both imido complexes. The inverse trans-influence was thus proven to be a key factor for the coordination mode of a terminal ligand on high valent uranium complexes. L III XANES was shown to be a great tool for the determination of oxidation states of uranium complexes. Therefore, a series of uranium complexes in all stable oxidation states for uranium, +III to +VI was prepared, and their spectra analyzed. All compounds bear only O-donor ligands in addition to the chlating trisaryloxide-tacn-ligand. A separation of 1.5 to 3 eV in the white line energy is observed between the different oxidation states. This series can be used as reference for compounds, where oxidation state assignment is not obvious, such as a ketyl radical complex [(( t-Bu Ar)O 3 tacn)U(O-C( t-Bu Ph) 2 .- )]. For this complex, the oxidation state of +IV could be assigned. Moreover, a series of isostructural uranium(IV) complexes was prepared. The influence of different ligands according to the spectrochemical series on the electronic and magnetic properties could be shown using UV/vis/NIR spectroscopy and variable temperature SQUID measurements. Calculations of uranium L III XANES spectra show a variation in the shape of the spectra and thus high resolution PFY-XANES would be a great tool to determine the electronic influence of these different axial ligands. Using the single N-anchored ligand system, the first

Determination of uranium by an amperometric method

International Nuclear Information System (INIS)

John, Mary; Venkataramana, P.; Vaidyanathan, S.; Natarajan, P.R.

1981-01-01

An amperometric method has been standardised for the determination of uranium. Uranium is reduced to its quadrivalent state in concentrated phosphoric acid medium with ferrous iron. The excess iron is destroyed with nitric acid in presence of Mo(VI). The medium is diluted and U(IV) is titrated with standard potassium dichromate to an amperometric end point using a pair of identical plantinum wires as electrodes. The reagent volumes and uranium quantities have been scaled down to 30 ml. and 2-5 mg of uranium in the present work with a view to minimising the problems associated with recovery of plutonium. The results are quantitative with an R.S.D. of 0.2% in the present version of weight based titrations. (author)

A Preliminary Study for Development of Amidoxime-functionalized Silica Adsorbents for Uranium(IV) Extraction from Seawater

Energy Technology Data Exchange (ETDEWEB)

Lee, Minseok; Ryu, Ho Jin [KAIST, Daejeon (Korea, Republic of)

2016-10-15

4 billion tons of uranium, which can supply the electricity for tens of thousands of years, is contained in seawater. Therefore, development of techniques for uranium sequestering from the ocean has been regarded as a great challenging for making nuclear energy to be more economical and sustainable. Despite the inexhaustible uranium resource, it is still hard to produce uranium economically from seawater due to its extremely low level of concentration (3.0 μg/L) and stable complex chemical formation, UO{sub 2}(CO3)34-. Various methods for uranium extraction from seawater have been suggested such as precipitation, solvent extraction, ion exchange, adsorption and etc. The most preferred method for extracting uranium is adsorption due to ease of separation from the liquid phase, environment friendliness and cost-effectiveness. Organic or inorganic solids functionalized with amidoxime (AO, -R-C(NH2)=NOH) groups, which has high affinity to uranium species, is the one of candidate material for uranium adsorbents. For long-term nuclear power generation, developing uranium extraction technologies from seawater has been a crucial issue. AO-based adsorbent has been considered as the most effective methods for uranium extraction from seawater, and collaboration with nanotechnology has been tried to enhance the traditional adsorbents, recently. Despite the attempts, most AO-based adsorbents were suffered from complexation of uranyl ions with carbonate ions and under the effect of pH. To achieve more efficient uranium uptake, bi-functionalized mesoporous silica with AO group and acidic groups was chosen as a model for this study.

Cyclopentadienyl complexes of uranium(IV) chlorides. Crystal structures of trichloro(eta5-cyclopentadienyl)bis(triphenylphosphine oxide)uranium(IV) tetrahydrofuran solvate and of trichloro(eta5-cyclopentadienyl)bis(hexamethylphosphoramide)uranium(IV)

International Nuclear Information System (INIS)

Bagnall, K.W.; De Paoli, G.

1984-01-01

The crystal and molecular structures of [U(cp)Cl 3 (PPh 3 O) 2 ].thf (thf = tetrahydrofuran) (1) and [U(cp)Cl 3 (P(NMe 2 ) 3 O) 2 ] (cp = eta 5 -cyclopentadienyl) (2) have been determined from three-dimensional X-ray diffraction data. The results are presented. In both compounds the uranium atom is octahedrally co-ordinated with the two neutral ligands [PPh 3 O and P(NMe 2 ) 3 O] in cis positions; the chlorine atoms are in the mer arrangement and the cyclopentadienyl group is trans to one neutral ligand. The appearance of cis octahedral geometry in complexes of the type [U(cp)Cl 3 L 2 ] is discussed in terms of the operation of a possible trans effect. (author)

Effects of nitrate on the stability of uranium in a bioreduced region of the subsurface

International Nuclear Information System (INIS)

Wu, Weimin; Carley, Jack M.; Green, Stefan; Luo, Jian; Kelly, Shelly D.; Van Nostrand, Joy; Lowe, Kenneth Alan; Mehlhorn, Tonia L.; Carroll, Sue L.; Boonchayanant, Benjaporn; Loeffler, Frank E.; Jardine, Philip M.; Criddle, Craig

2010-01-01

The effects of nitrate on the stability of reduced, immobilized uranium were evaluated in field experiments at a U.S. Department of Energy site in Oak Ridge, TN. Nitrate (2.0 mM) was injected into a reduced region of the subsurface containing high levels of previously immobilized U(IV). The nitrate was reduced to nitrite, ammonium, and nitrogen gas; sulfide levels decreased; and Fe(II) levels increased then deceased. Uranium remobilization occurred concomitant with nitrite formation, suggesting nitrate-dependent, iron-accelerated oxidation of U(IV). Bromide tracer results indicated changes in subsurface flowpaths likely due to gas formation and/or precipitate. Desorption-adsorption of uranium by the iron-rich sediment impacted uranium mobilization and sequestration. After rereduction of the subsurface through ethanol additions, background groundwater containing high levels of nitrate was allowed to enter the reduced test zone. Aqueous uranium concentrations increased then decreased. Clone library analyses of sediment samples revealed the presence of denitrifying bacteria that can oxidize elemental sulfur, H 2 S, Fe(II), and U(IV) (e.g., Thiobacillus spp.), and a decrease in relative abundance of bacteria that can reduce Fe(III) and sulfate. XANES analyses of sediment samples confirmed changes in uranium oxidation state. Addition of ethanol restored reduced conditions and triggered a short-term increase in Fe(II) and aqueous uranium, likely due to reductive dissolution of Fe(III) oxides and release of sorbed U(VI). After two months of intermittent ethanol addition, sulfide levels increased, and aqueous uranium concentrations gradually decreased to <0.1 μM.

Determination of uranium by a gravimetric-volumetric titration method

International Nuclear Information System (INIS)

Krtil, J.

1998-01-01

A volumetric-gravimetric modification of a method for the determination of uranium based on the reduction of uranium to U (IV) in a phosphoric acid medium and titration with a standard potassium dichromate solution is described. More than 99% of the stoichiometric amount of the titrating solution is weighed and the remainder is added volumetrically by using the Mettler DL 40 RC Memotitrator. Computer interconnected with analytical balances collects continually the data on the analyzed samples and evaluates the results of determination. The method allows to determine uranium in samples of uranium metal, alloys, oxides, and ammonium diuranate by using aliquot portions containing 30 - 100 mg of uranium with the error of determination, expressed as the relative standard deviation, of 0.02 - 0.05%. (author)

The hydrolysis of thorium dicarbide and of mixed uranium-thorium dicarbides

International Nuclear Information System (INIS)

Del Litto, B.

1966-09-01

The hydrolysis of thorium dicarbide leads to the formation of a complex mixture of gaseous and condensed carbon hydrides. The temperature, between 25 and 100 deg. C, has no influence on the nature and composition of the gas phase. The reaction kinetics, however, are strongly temperature dependent. In a hydrochloric medium, an enrichment in hydrogen of the gas mixture is observed. On the other hand a decrease in hydrogen and an increase in acetylene content take place in an oxidizing medium. The general results can be satisfactorily interpreted through a reaction mechanism involving C-C radical groups. In the same way, the hydrolysis of uranium-thorium-carbon ternary alloys leads to the formation of gaseous and condensed carbon hydrides. The variation of the composition of the gas phase versus uranium content in the alloy suggests an hypothesis about the carbon-carbon distance in the alloy crystal lattice. The variation of methane content, on the other hand, has lead us to discuss the nature of the various phases present in uranium-carbon alloys and carbon-rich uranium-thorium-carbon alloys. We have reached the conclusion that these alloys include a proportion of monocarbide which is dependent upon the ratio. Th/(Th + U). We put forward a diagram of the system uranium-carbon with features proper to explain some phenomena which have been observed in the uranium-thorium-carbon ternary diagram. (author) [fr

Understanding Uranium Behavior in a Reduced Aquifer

Science.gov (United States)

Janot, N.; Lezama-Pacheco, J. S.; Williams, K. H.; Bernier-Latmani, R.; Long, P. E.; Davis, J. A.; Fox, P. M.; Yang, L.; Giammar, D.; Cerrato, J. M.; Bargar, J.

2012-12-01

Uranium contamination of groundwater is a concern at several US Department of Energy sites, such Old Rifle, CO. Uranium transport in the environment is mainly controlled by its oxidation state, since oxidized U(VI) is relatively mobile, whereas U(IV) is relatively insoluble. Bio-remediation of contaminated aquifers aims at immobilizing uranium in a reduced form. Previous laboratory and field studies have shown that adding electron donor (lactate, acetate, ethanol) to groundwater stimulates the activity of metal- and sulfate-reducing bacteria, which promotes U(VI) reduction in contaminated aquifers. However, obtaining information on chemical and physical forms of U, Fe and S species for sediments biostimulated in the field, as well as kinetic parameters such as U(VI) reduction rate, is challenging due to the low concentration of uranium in the aquifers (typically bio-remediation experiment at the Old Rifle site, CO, from early iron-reducing conditions to the transition to sulfate-reducing conditions. Several in-well chromatographic columns packed with sediment were deployed and were sampled at different days after the start of bio-reduction. X-ray absorption spectroscopy and X-ray microscopy were used to obtain information on Fe, S and U speciation and distribution. Chemical extractions of the reduced sediments have also been performed, to determine the rate of Fe(II) and U(IV) accumulation.

Uranium geochemistry of Orca Basin

International Nuclear Information System (INIS)

Weber, F.F. Jr.; Sackett, W.M.

1981-01-01

Orca Basin, an anoxic, brine-filled depression at a depth of 2200 m in the Northwestern Gulf of Mexico continental slope, has been studied with respect to its uranium geochemistry. Uranium concentration profiles for four cores from within the basin were determined by delayed-neutron counting. Uranium concentrations ranged from 2.1 to 4.1 ppm on a salt-free and carbonate-corrected basis. The highest uranium concentrations were associated with the lowest percentage and delta 13 C organic carbon values. For comparison, cores from the brine-filled Suakin and Atlantis II Deeps, both in the Red Sea, were also analyzed. Uranium concentrations ranged from 1.2 to 2.6 ppm in the Suakin Deep and from 8.0 to 11.0 ppm in the Atlantis II Deep. No significant correlation was found between uranium concentrations and organic carbon concentrations and delta 13 C values for these cores. Although anoxic conditions are necessary for significant uranium uptake by non-carbonate marine sediments, other factors such as dilution by rapidly depositing materials and uranium supply via mixing and diffusion across density gradients may be as important in determining uranium concentrations in hypersaline basin sediments. (author)

Stability constants of mixed ligand complexes of dioxouranium(II) and thorium(IV) with complexones and isomeric alanines

International Nuclear Information System (INIS)

Singh, R.K.; Saxena, M.C.

1992-01-01

The present work reports on the stability sequence between UO 2 II and Th IV ions for their mixed ligands complexes with the two isomeric alanines, α-alanine (α-ala) and β-alanine (β-ala) containing a complexone as primary ligand. The complexones used are iminodiacetate (IMDA), nitrilotricetate (NTA), 2-hydroxyethylenediaminetriacetate (HEDTA), ethylenediaminetetraacetate (EDTA), 1,2-diaminocyclohexanetraacetate (CDTA) and diethylenetriminepentaacetate (DTPA). (author). 9 refs., 1 tab

Uranium-series constraints on radionuclide transport and groundwater flow at the Nopal I uranium deposit, Sierra Pena Blanca, Mexico.

Science.gov (United States)

Goldstein, Steven J; Abdel-Fattah, Amr I; Murrell, Michael T; Dobson, Patrick F; Norman, Deborah E; Amato, Ronald S; Nunn, Andrew J

2010-03-01

Uranium-series data for groundwater samples from the Nopal I uranium ore deposit were obtained to place constraints on radionuclide transport and hydrologic processes for a nuclear waste repository located in fractured, unsaturated volcanic tuff. Decreasing uranium concentrations for wells drilled in 2003 are consistent with a simple physical mixing model that indicates that groundwater velocities are low ( approximately 10 m/y). Uranium isotopic constraints, well productivities, and radon systematics also suggest limited groundwater mixing and slow flow in the saturated zone. Uranium isotopic systematics for seepage water collected in the mine adit show a spatial dependence which is consistent with longer water-rock interaction times and higher uranium dissolution inputs at the front adit where the deposit is located. Uranium-series disequilibria measurements for mostly unsaturated zone samples indicate that (230)Th/(238)U activity ratios range from 0.005 to 0.48 and (226)Ra/(238)U activity ratios range from 0.006 to 113. (239)Pu/(238)U mass ratios for the saturated zone are 1000 times lower than the U mobility. Saturated zone mobility decreases in the order (238)U approximately (226)Ra > (230)Th approximately (239)Pu. Radium and thorium appear to have higher mobility in the unsaturated zone based on U-series data from fractures and seepage water near the deposit.

Uranium-series constraints on radionuclide transport and groundwater flow at the Nopal I uranium deposit, Sierra Pena Blanca, Mexico

International Nuclear Information System (INIS)

Goldstein, S.J.; Abdel-Fattah, A.I.; Murrell, M.T.; Dobson, P.F.; Norman, D.E.; Amato, R.S.; Nunn, A.J.

2009-01-01

Uranium-series data for groundwater samples from the Nopal I uranium ore deposit were obtained to place constraints on radionuclide transport and hydrologic processes for a nuclear waste repository located in fractured, unsaturated volcanic tuff. Decreasing uranium concentrations for wells drilled in 2003 are consistent with a simple physical mixing model that indicates that groundwater velocities are low (∼10 m/y). Uranium isotopic constraints, well productivities, and radon systematics also suggest limited groundwater mixing and slow flow in the saturated zone. Uranium isotopic systematics for seepage water collected in the mine adit show a spatial dependence which is consistent with longer water-rock interaction times and higher uranium dissolution inputs at the front adit where the deposit is located. Uranium-series disequilibria measurements for mostly unsaturated zone samples indicate that 230 Th/ 238 U activity ratios range from 0.005-0.48 and 226 Ra/ 238 U activity ratios range from 0.006-113. 239 Pu/ 238 U mass ratios for the saturated zone are -14 , and Pu mobility in the saturated zone is >1000 times lower than the U mobility. Saturated zone mobility decreases in the order 238 U∼ 226 Ra > 230 Th∼ 239 Pu. Radium and thorium appear to have higher mobility in the unsaturated zone based on U-series data from fractures and seepage water near the deposit.

Synthesis and insertion chemistry of mixed tether uranium metallocene complexes

Energy Technology Data Exchange (ETDEWEB)

Siladke, Nathan A.; LeDuc, Jennifer; Ziller, Joseph W.; Evans, William J. [Department of Chemistry, University of California, Irvine, CA (United States)

2012-11-12

The synthesis of mixed tethered alkyl uranium metallocenes has been investigated by examining the reactivity of the bis(tethered alkyl) metallocene [(η{sup 5}-C{sub 5}Me{sub 4}SiMe{sub 2}CH{sub 2}-κC){sub 2}U] (1) with substrates that react with only one of the U-C linkages. The effect of these mixed tether coordination environments on the reactivity of the remaining U-C bond has been studied by using CO insertion chemistry. One equivalent of azidoadamantane (AdN{sub 3}) reacts with 1 to yield the mixed tethered alkyl triazenido complex [(η{sup 5}-C{sub 5}Me{sub 4}SiMe{sub 2}CH{sub 2}-κC)U(η{sup 5}-C{sub 5}Me{sub 4}SiMe{sub 2}-CH{sub 2}NNN-Ad-κ{sup 2}N{sup 1,3})]. Similarly, a single equivalent of CS{sub 2} reacts with 1 to form the mixed tethered alkyl dithiocarboxylate complex [(η{sup 5}-C{sub 5}Me{sub 4}SiMe{sub 2}CH{sub 2}-κC)U(η{sup 5}-C{sub 5}Me{sub 4}SiMe{sub 2}- CH{sub 2}C(S){sub 2}-κ{sup 2}S,S{sup '})], a reaction that constitutes the first example of CS{sub 2} insertion into a U{sup 4+}-C bond. Complex 1 reacts with one equivalent of pyridine N-oxide by C-H bond activation of the pyridine ring to form a mixed tethered alkyl cyclometalated pyridine N-oxide complex [(η{sup 5}-C{sub 5}Me{sub 4}SiMe{sub 2}CH{sub 2}-κC)(η{sup 5}-C{sub 5}Me{sub 4}SiMe{sub 3})U(C{sub 6}H{sub 4}NO-κ{sup 2} C,O)]. The remaining (η{sup 5}-C{sub 5}Me{sub 4}SiMe{sub 2}CH{sub 2}-κC){sup 2-} ligand in each of these mixed tethered species show reactivity towards CO and tethered enolate ligands form by insertion. Subsequent rearrangement have been identified in [(η{sup 5}-C{sub 5}Me{sub 4}SiMe{sub 3})U(C{sub 5}H{sub 4}NO-κ{sup 2}C,O)(η{sup 5}-C{sub 5}Me{sub 4}SiMe{sub 2}C(=CH{sub 2})O- κO)] and [(η{sup 5}-C{sub 5}Me{sub 4}SiMe{sub 2}CH{sub 2}NNN-Ad-κ{sup 2}N{sup 1,3})U(η{sup 5}-C{sub 5}Me{sub 4}SiMe{sub 2}C(=CH{sub 2})O-κO)]. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Technical data summary: Uranium(IV) production using a large scale electrochemical cell

International Nuclear Information System (INIS)

Hsu, T.C.

1984-05-01

This Technical Data Summary outlines an electrochemical process to produce U(IV), in the form of uranous nitrate, from U(VI), as uranyl nitrate. U(IV) with hydrazine could then be used as an alternative plutonium reductant to substantially reduce the waste volume from the Purex solvent extraction process. This TDS is divided into three parts. The first part (Chapters I to IV) generally describes the electrochemical production of U(IV). The second part (Chapters V to VII) describes a pilot scale U(IV) production facility that was constructed and operated at an engineering semiworks area of SRP, referred to as TNX. The lst part (Chapter VIII) describes a preliminary design for a full-scale facility that would meet the projected need for U(IV) as a reductant in SRP's separations processes. The preliminary design was described in a Basic Data Summary for the U(IV) production facility, and a Venture Guidance Appraisal (VGA) was prepared from the Basic Data Summary. The VGA for the U(IV) process showed that because of the large capital investment required, this approach to waste reduction was not economically competitive with another alternative that required only modifying the ongoing Purex process at no additional capital cost. However, implementing he U(IV) process as part of an overall canyon renovation, presently scheduled for the 1990's, may be economically attractive. The purpose of this TDS is therefore to bring together the information and experience obtained thus far in the U(IV) program so that a useful body of information will be available to support any future development of this process

Potential Aquifer Vulnerability in Regions Down-Gradient from Uranium In Situ Recovery (ISR) Sites

Science.gov (United States)

Sandstone-hosted roll-front uranium ore deposits originate when U(VI) dissolved in groundwater is reduced and precipitated as insoluble U(IV) minerals. Groundwater redox geochemistry, aqueous complexation, and solute migration are instrumental in leaching uranium from source rock...

Determination of traces of uranium in sea water after separation by froth flotation

International Nuclear Information System (INIS)

Sekine, K.

1975-01-01

Uranium in sea water is separated by froth flotation of the uranium (VI)-Arsenazo III-Zephiramine ion-adduct and then determined by neutron activation or spectrophotometric method using the uranium(IV)-Arsenazo III complex. Results of the analysis of Pacific coastal samples by the two methods are in good agreement; an average value of 3.0μg U/per liter was obtained. (author)

Uranium Biominerals Precipitated by an Environmental Isolate of Serratia under Anaerobic Conditions

Science.gov (United States)

Newsome, Laura; Morris, Katherine; Lloyd, Jonathan. R.

2015-01-01

Stimulating the microbially-mediated precipitation of uranium biominerals may be used to treat groundwater contamination at nuclear sites. The majority of studies to date have focussed on the reductive precipitation of uranium as U(IV) by U(VI)- and Fe(III)-reducing bacteria such as Geobacter and Shewanella species, although other mechanisms of uranium removal from solution can occur, including the precipitation of uranyl phosphates via bacterial phosphatase activity. Here we present the results of uranium biomineralisation experiments using an isolate of Serratia obtained from a sediment sample representative of the Sellafield nuclear site, UK. When supplied with glycerol phosphate, this Serratia strain was able to precipitate 1 mM of soluble U(VI) as uranyl phosphate minerals from the autunite group, under anaerobic and fermentative conditions. Under phosphate-limited anaerobic conditions and with glycerol as the electron donor, non-growing Serratia cells could precipitate 0.5 mM of uranium supplied as soluble U(VI), via reduction to nano-crystalline U(IV) uraninite. Some evidence for the reduction of solid phase uranyl(VI) phosphate was also observed. This study highlights the potential for Serratia and related species to play a role in the bioremediation of uranium contamination, via a range of different metabolic pathways, dependent on culturing or in situ conditions. PMID:26132209

Fate of Uranium in Wetlands: Impact of Drought Followed by Re-flooding

Science.gov (United States)

Gilson, E.; Huang, S.; Koster van Groos, P. G.; Scheckel, K.; Peacock, A. D.; Kaplan, D. I.; Jaffe, P. R.

2014-12-01

Uranium contamination in groundwater can be mitigated in anoxic zones by iron-reducing bacteria that reduce soluble U(VI) to insoluble U(IV) and by uranium immobilization through complexation and sorption. Wetlands often link ground and surface-waters, making them strategic systems for potentially limiting migration of uranium contamination. Little is known about how drought periods that result in the drying of wetland soils, and consequent redox changes, affect uranium fate and transport in wetlands. In order to better understand the fate and stability of immobilized uranium in wetland soils, and how dry periods affect the uranium stability, we dosed saturated wetland mesocosms planted with Scirpus acutus with low levels of uranyl-acetate for 5 months before imposing a 9-day drying period followed by a 13-day rewetting period. Concentrations of uranium in mesocosm effluent increased after rewetting, but the cumulative amount of uranium released in the 13 days following the drying constituted less than 1% of the uranium immobilized in the soil during the 5 months prior to the drought. This low level of remobilization suggests that the uranium immobilized in these soils was not primarily bioreduced U(IV), which could have been oxidized to soluble U(VI) during the drought and released in the effluent during the subsequent flood. XANES analyses confirm that most of the uranium immobilized in the mesocosms was U(VI) sorbed to iron oxides. Compared to mesocosms that did not experience drying or rewetting, mesocosms that were sacrificed immediately after drying and after 13 days of rewetting had less uranium in soil near roots and more uranium on root surfaces. Metal-reducing bacteria only dominated the bacterial community after 13 days of rewetting and not immediately after drying, indicating that these bacteria are not responsible for this redistribution of uranium after the drying and rewetting. Results show that short periods of drought conditions in a wetland may

Electrochemical investigation of tetravalent uranium β-diketones for active materials of all-uranium redox flow battery

International Nuclear Information System (INIS)

Yamamura, Tomoo; Shiokawa, Yoshinobu; Ikeda, Yasuhisa

2002-01-01

For active materials of the all-uranium redox flow battery for the power storage, tetravalent uranium β-diketones were investigated. The electrode reactions of U(ba) 4 and U(btfa) 4 were examined in comparison with that of U(acac) 4 , where ba denotes benzoylacetone, btfa benzoyltrifluoroacetone and acac acetylacetone. The cyclic voltammograms of U(ba) 4 and U(btfa) 4 solutions indicate that there are two series of redox reactions corresponding to the complexes with different coordination numbers of four and three. The electrode kinetics of the U(IV)/U(III) redox reactions for btfa complexes is examined. The obtained result supports that the uranium β-diketone complexes examined in the present study will serve as excellent active materials for negative electrolyte in the redox flow battery. (author)

A Highly Expressed High-Molecular-Weight S-Layer Complex of Pelosinus sp. Strain UFO1 Binds Uranium

Energy Technology Data Exchange (ETDEWEB)

Thorgersen, Michael P. [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemistry and Molecular Biology; Lancaster, W. Andrew [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemistry and Molecular Biology; Rajeev, Lara [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Biological Systems and Engineering Division; Ge, Xiaoxuan [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemistry and Molecular Biology; Vaccaro, Brian J. [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemistry and Molecular Biology; Poole, Farris L. [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemistry and Molecular Biology; Arkin, Adam P. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Biological Systems and Engineering Division; Mukhopadhyay, Aindrila [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Biological Systems and Engineering Division; Adams, Michael W. W. [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemistry and Molecular Biology

2016-12-02

Cell suspensions of Pelosinus sp. strain UFO1 were previously shown, using spectroscopic analysis, to sequester uranium as U(IV) complexed with carboxyl and phosphoryl group ligands on proteins. The goal of our present study was to characterize the proteins involved in uranium binding. Virtually all of the uranium in UFO1 cells was associated with a heterodimeric protein, which was termed the uranium-binding complex (UBC). The UBC was composed of two S-layer domain proteins encoded by UFO1_4202 and UFO1_4203. Samples of UBC purified from the membrane fraction contained 3.3 U atoms/heterodimer, but significant amounts of phosphate were not detected. The UBC had an estimated molecular mass by gel filtration chromatography of 15 MDa, and it was proposed to contain 150 heterodimers (UFO1_4203 and UFO1_4202) and about 500 uranium atoms. The UBC was also the dominant extracellular protein, but when purified from the growth medium, it contained only 0.3 U atoms/heterodimer. The two genes encoding the UBC were among the most highly expressed genes within the UFO1 genome, and their expressions were unchanged by the presence or absence of uranium. Therefore, the UBC appears to be constitutively expressed and is the first line of defense against uranium, including by secretion into the extracellular medium. Although S-layer proteins were previously shown to bind U(VI), here we showed that U(IV) binds to S-layer proteins, we identified the proteins involved, and we quantitated the amount of uranium bound. Widespread uranium contamination from industrial sources poses hazards to human health and to the environment. Here in this paper, we identified a highly abundant uranium-binding complex (UBC) from Pelosinus sp. strain UFO1. The complex makes up the primary protein component of the S-layer of strain UFO1 and binds 3.3 atoms of U(IV) per heterodimer. Finally, while other bacteria have been shown to bind U(VI) on their S-layer, we demonstrate here an example of U(IV) bound by

Biosolubilization of uranyl ions in uranium ores by hydrophyte plants

International Nuclear Information System (INIS)

Cecal, Alexandru; Calmoi, Rodica; Melniciuc-Puica, Nicoleta

2006-01-01

This paper investigated the bioleaching of uranyl ions from uranium ores, in aqueous medium by hydrophyte plants: Lemna minor, Azolla caroliniana and Elodea canadensis under different experimental conditions. The oxidation of U(IV) to U(VI) species was done by the atomic oxygen generated in the photosynthesis process by the aquatic plants in the solution above uranium ores. Under identical experimental conditions, the capacity of bioleaching of uranium ores decreases according to the following series: Lemna minor > Elodea canadensis > Azolla caroliniana. The results of IR spectra suggest the possible use of Lemna minor and Elodea canadensis as a biological decontaminant of uranium containing wastewaters. (author)

Bent and linear Uranium(IV) metallocenes with terminal and bridging cyanide ligands

International Nuclear Information System (INIS)

Maynadie, J.; Berthet, J.C.; Thuery, P.; Ephritikhine, M.

2007-01-01

Treatment of Cp 2 * UI 2 with KCN in thf led to the formation of Cp 2 * U(CN) 2 (2), which further reacted with NR 4 CN to give [Cp 2 * U(CN) 3 ][ NR 4 ] (R = Et, 3; R = n Bu, 3') and [Cp 2 * U(CN) 5 ][NR 4 ] 3 (R = Et, 4; R n Bu, 4'). While the tri-cyanide 3' adopts the familiar bent sandwich configuration, the penta-cyanide 4 is, after the [Cp 2 * U(NCMe) 5 ] 2+ cation, the second example of a linear metallocene resulting from complete saturation of the equatorial girdle. Compound 3' was also obtained by oxidation of the trivalent compound [Cp 2 * U(CN) 3 ][N n Bu 4 ] 2 ; the rapid and reversible electron transfer between the U(III) and U(IV) complexes was revealed by 1 H NMR spectroscopy. The NMR spectra also revealed that 4 is partially dissociated in thf into 3, providing the first example of an equilibrating couple of bent and linear metallocenes [K = 4.24(4) * 10 -5 at 25 C, ΔH = 199(6) kJ mol -1 , and ΔS = 586(20) J mol -1 K -1 ]. The trinuclear compound [Cp 2 * UCl 2 (μ-CN)] 2 Mg(thf) 4 (1) and the 2D polymeric complex [Cp 2 * U(dmf) 3 -(μ-NC) 2 (AgI) 2 ] n (5), which were obtained during initial attempts on the synthesis of 2-4 and uranium- (V) derivatives, exhibit a bent and linear sandwich structure, respectively. (authors)

NURE uranium deposit model studies

International Nuclear Information System (INIS)

Crew, M.E.

1981-01-01

The National Uranium Resource Evaluation (NURE) Program has sponsored uranium deposit model studies by Bendix Field Engineering Corporation (Bendix), the US Geological Survey (USGS), and numerous subcontractors. This paper deals only with models from the following six reports prepared by Samuel S. Adams and Associates: GJBX-1(81) - Geology and Recognition Criteria for Roll-Type Uranium Deposits in Continental Sandstones; GJBX-2(81) - Geology and Recognition Criteria for Uraniferous Humate Deposits, Grants Uranium Region, New Mexico; GJBX-3(81) - Geology and Recognition Criteria for Uranium Deposits of the Quartz-Pebble Conglomerate Type; GJBX-4(81) - Geology and Recognition Criteria for Sandstone Uranium Deposits in Mixed Fluvial-Shallow Marine Sedimentary Sequences, South Texas; GJBX-5(81) - Geology and Recognition Criteria for Veinlike Uranium Deposits of the Lower to Middle Proterozoic Unconformity and Strata-Related Types; GJBX-6(81) - Geology and Recognition Criteria for Sandstone Uranium Deposits of the Salt Wash Type, Colorado Plateau Province. A unique feature of these models is the development of recognition criteria in a systematic fashion, with a method for quantifying the various items. The recognition-criteria networks are used in this paper to illustrate the various types of deposits

Study on reduction and back extraction of Pu(IV) by urea derivatives in nitric acid conditions

International Nuclear Information System (INIS)

Ye, G.A.; Xiao, S.T.; Yan, T.H.; Lin, R.S.; Zhu, Z.W.

2013-01-01

The reduction kinetics of Pu(IV) by hydroxyl-semicarbazide (HSC), hydroxyurea (HU) and di-hydroxyurea (DHU) in nitric acid solutions were investigated separately with adequate kinetic equations. In addition, counter-current cascade experiments were conducted for Pu split from U in nitric acid media using three kinds of reductant, respectively. The results show that urea derivatives as a kind of novel salt-free reductant can reduce Pu(IV) to Pu(III) rapidly in the nitric acid solutions. The stripping experimental results showed that Pu(IV) in the organic phase can be stripped rapidly to the aqueous phase by the urea derivatives, and the separation factors of plutonium /uranium can reach more than 10 4 . This indicates that urea derivatives is a kind of promising salt-free agent for uranium/plutonium separation. In addition, the complexing effect of HSC with Np(IV) was revealed, and Np(IV) can be back-extracted by HSC with a separation factor of about 20

Study on reduction and back extraction of Pu(IV) by urea derivatives in nitric acid conditions

Energy Technology Data Exchange (ETDEWEB)

Ye, G.A.; Xiao, S.T.; Yan, T.H.; Lin, R.S.; Zhu, Z.W. [China Institute of Atomic Energy, P.O.Box 275(26), Beijing 102413 (China)

2013-07-01

The reduction kinetics of Pu(IV) by hydroxyl-semicarbazide (HSC), hydroxyurea (HU) and di-hydroxyurea (DHU) in nitric acid solutions were investigated separately with adequate kinetic equations. In addition, counter-current cascade experiments were conducted for Pu split from U in nitric acid media using three kinds of reductant, respectively. The results show that urea derivatives as a kind of novel salt-free reductant can reduce Pu(IV) to Pu(III) rapidly in the nitric acid solutions. The stripping experimental results showed that Pu(IV) in the organic phase can be stripped rapidly to the aqueous phase by the urea derivatives, and the separation factors of plutonium /uranium can reach more than 10{sup 4}. This indicates that urea derivatives is a kind of promising salt-free agent for uranium/plutonium separation. In addition, the complexing effect of HSC with Np(IV) was revealed, and Np(IV) can be back-extracted by HSC with a separation factor of about 20.

Tris[bis(trimethylsilyl)amido]uranium: Compounds with tri-, tetra-, and penta-valent uranium

International Nuclear Information System (INIS)

Stewart, J.L.

1988-04-01

This trivalent uranium compound, serves as a precursor to new tri-, tetra-, and penta-valent uranium species. The geometry about the U atom is pyramidal. Lewis-base coordination compounds of U[N(SiMe 3 ) 2 ] 3 with a one-to-one- ratio of Lewis base to uranium were isolated with pyridine, 4-dimethylamino-pyridine, 2,6-Me 2 -C 6 H 3 NC, and TPO. Two-to-one coordination compounds were obtained with t-butylnitrile and t-butylisocyanide. Compounds with more sterically demanding bases could not be isolated. The expected decrease in U-N(SiMe 3 ) 2 bond length with increase in oxidation state is not observed. Reaction of ClU[N(SiMe 3 ) 2 ] 3 and Li[NH(p-tolyl)] yields the uranium (IV) dimer, U 2 [N(SiMe 3 ) 2 ] 4 [μ-N(p-tolyl)] 2 . Reaction with 2,4,6-triemethylaniline produces a dimer. Analogous substitution products could not be obtained with aniline or p-toluidine. t-Bu 3 CO/sup /minus//, t-Bu 2 CHO/sup /minus//, and t-Bu 3 SiO/sup /minus// are used to synthesize new tetravalent, mononuclear uranium compounds. Reaction of ClU(tritox) 3 with alkyllithium reagents leads to isolation of RU(tritox) 3 . The reaction of U(ditox) 4 with MeLi affords the addition product U(ditox) 4 (Me)Li, whose crystal structure is described. Preparation of uranium silox compounds is reported. 97 refs., 26 figs., 39 tabs

Granite-related hypothermal uranium mineralization in South China

International Nuclear Information System (INIS)

Liu, X.; Wu, J.; Pan, J.; Zhu, M.

2014-01-01

As one of the important geological types, granite-related uranium deposits account for about 29% of the total discovered natural uranium resources in China. Most of the granite-related uranium deposits located in Taoshan - Zhuguang uranium metallogenic belt, South China. In addition to the typical pitchblende vein-type uranium mineralization of epithermal metallogenic system, a new type of granite-related uranium mineralization with characteristics of hypothermal matallogenic system was discovered in South China by current studies. However, hypothermal is contact thermal to epithermal mineralization, and not the conventional intrusive high temperature mineralization. Hypothermal uranium mineralization is presented by disseminated uraninite or pitchblende stockwork in fissures in granites normally with extensive alkaline alteration. The high temperature mineral assemblage of uraninite associate with scheelite and tourmaline was identified in hypothermal uranium mineralization. Fluid inclusion studies on this type mineralization indicated the middle to high temperature (>250℃) mineralization with the mixing evidence of ore forming solution derived from deep level, and the boiling and mixing of ore forming solution are regarded as the dominant mineralization mechanism for the precipitating of uranium. In contrast to the mineralization ages of 67 Ma to 87 Ma for typical pitchblende vein mineralization of epithermal metallogenic system, the mineralization age is older than 100 Ma for hypothermal uranium mineralization in granite. In the Shituling deposit, Xiazhuang uranium ore field, uraninite and pitchblende micro veins with extensive potassic alteration, chloritization and sericitization are hosted in fissures of Indo-Chinese epoch granites with the uranium mineralization age of 130 Ma to 138 Ma with a mineralization temperature of 290℃ to 330℃ indicated. Other examples sharing the similar characters of hypothermal uranium mineralization have been recognized in

A new method for dosing uranium in biological media; Nouvelle methode de dosage de l'uranium dans les milieux biologiques

Energy Technology Data Exchange (ETDEWEB)

Henry, Ph; Kobisch, Ch [Commissariat a l' Energie Atomique, Centre de Production de Plutonium, Marcoule (France). Centre d' Etudes Nucleaires

1964-07-01

This report describes a new method for dosing uranium in biological media based on measurement of alpha activity. After treatment of the sample with a mineral acid, the uranium is reduced to the valency four by trivalent titanium and is precipitated as phosphate in acid solution. The uranium is then separated from the titanium by precipitation as UF{sub 4} with lanthanum as carrier. A slight modification, unnecessary in the case of routine analyses, makes it possible to eliminate other possible alpha emitters (thorium and transuranic elements). (authors) [French] Ce rapport decrit une nouvelle methode de dosage de l'uranium dans les milieux biologiques par mesure de l'activite alpha. Apres mineralisation de l'echantillon, l'uranium est reduit a la valence IV par le titane trivalent et precipite en milieu acide sous forme de phosphate. L'uranium est ensuite separe du titane par precipitation a l'etat d'UF{sub 4} avec du lanthane entraineur. Une legere modification, inutile dans le cas d'analyses de routine, permet d'effectuer l'elimination d'autres emetteurs alpha eventuels (thorium et transuraniens). (auteurs)

Uranium-series constraints on radionuclide transport and groundwater flow at the Nopal I uranium deposit, Sierra Pena Blanca, Mexico

Energy Technology Data Exchange (ETDEWEB)

Goldstein, S.J.; Abdel-Fattah, A.I.; Murrell, M.T.; Dobson, P.F.; Norman, D.E.; Amato, R.S.; Nunn, A. J.

2009-10-01

Uranium-series data for groundwater samples from the Nopal I uranium ore deposit were obtained to place constraints on radionuclide transport and hydrologic processes for a nuclear waste repository located in fractured, unsaturated volcanic tuff. Decreasing uranium concentrations for wells drilled in 2003 are consistent with a simple physical mixing model that indicates that groundwater velocities are low ({approx}10 m/y). Uranium isotopic constraints, well productivities, and radon systematics also suggest limited groundwater mixing and slow flow in the saturated zone. Uranium isotopic systematics for seepage water collected in the mine adit show a spatial dependence which is consistent with longer water-rock interaction times and higher uranium dissolution inputs at the front adit where the deposit is located. Uranium-series disequilibria measurements for mostly unsaturated zone samples indicate that {sup 230}Th/{sup 238}U activity ratios range from 0.005-0.48 and {sup 226}Ra/{sup 238}U activity ratios range from 0.006-113. {sup 239}Pu/{sup 238}U mass ratios for the saturated zone are <2 x 10{sup -14}, and Pu mobility in the saturated zone is >1000 times lower than the U mobility. Saturated zone mobility decreases in the order {sup 238}U{approx}{sup 226}Ra > {sup 230}Th{approx}{sup 239}Pu. Radium and thorium appear to have higher mobility in the unsaturated zone based on U-series data from fractures and seepage water near the deposit.

Groundwater contamination from an inactive uranium mill tailings pile. 2. Application of a dynamic mixing model

International Nuclear Information System (INIS)

Narashimhan, T.N.; White, A.F.; Tokunaga, T.

1986-01-01

At Riverton, Wyoming, low pH process waters from an abandoned uranium mill tailings pile have been infiltrating into and contaminating the shallow water table aquifer. The contamination process has been governed by transient infiltration rates, saturated-unsaturated flow, as well as transient chemical reactions between the many chemical species present in the mixing waters and the sediments. In the first part of this two-part series the authors presented field data as well as an interpretation based on a static mixing models. As an upper bound, the authors estimated that 1.7% of the tailings water had mixed with the native groundwater. In the present work they present the results of numerical investigation of the dynamic mixing process. The model, DYNAMIX (DYNamic MIXing), couples a chemical speciation algorithm, PHREEQE, with a modified form of the transport algorithm, TRUMP, specifically designed to handle the simultaneous migration of several chemical constituents. The overall problem of simulating the evolution and migration of the contaminant plume was divided into three sub problems that were solved in sequential stages. These were the infiltration problem, the reactive mixing problem, and the plume-migration problem. The results of the application agree reasonably with the detailed field data. The methodology developed in the present study demonstrates the feasibility of analyzing the evolution of natural hydrogeochemical systems through a coupled analysis of transient fluid flow as well as chemical reactions. It seems worthwhile to devote further effort toward improving the physicochemical capabilities of the model as well as to enhance its computational efficiency

Formation of colloids of the tetravalent uranium under influence of silicate in neutral and low alkaline aqueous systems; Bildung von Kolloiden des tetravalenten Urans unter Einfluss von Silikat in neutralen und schwachalkalischen waessrigen Systemen

Energy Technology Data Exchange (ETDEWEB)

Ulbricht, Isabell

2016-03-30

This work includes the preparation and characterization of new uranium(IV) colloids which are formed and stabilized in the near neutral pH range and under environmentally relevant conditions. Conclusions on stability behavior and particle size distributions were drawn based on results obtained by dynamic light scattering, zeta potential measurements, as well as ultrafiltration and ultracentrifugation in combination with element analyzes. Spectroscopic methodes confirmed the tetravalent state of uranium in the experiments. Unlike empirical data, it is possible to generate long-term stable uranium(IV) colloids at higher concentrations. By addition of geochemical components such as carbonate and silicate, they are stable and resistant in the near neutral pH range over a long period. It was found that dissolved silica plays an essential role in the preparation of colloids. Colloid-borne uranium(IV) up to a concentration of 10{sup -3} mol/L, corresponding to 0,238 g/L, is stabilized in solutions. This concentration is about three orders of magnitude higher than so far known silicate-free aqueous uranium(IV) colloids. Through the use of different analytical methods (invasive and non-invasive) it could be shown that the resulting uranium(IV) colloids are in the nanoscalar range. A high mobility can be assumed in aquatic systems. Evidence is provided by photon correlation spectroscopy, ultrafiltration, and ultracentrifugation that uranium(IV) can form silicate-containing colloids of a size lower than 20 nm. The particles are generated in near neutral to slightly alkaline solutions containing geochemical relevant components (carbonate, silicate, sodium ions). They remain stable in aqueous suspension over years. Electrostatic repulsion due to a negative zeta potential in the near-neutral to alkaline pH range caused by the silicate stabilizes the uranium(IV) colloids. The isoelectric point of the nanoparticles is shifted towards lower pH values by the silicate. The higher the

Contribution to the study of liquid-liquid extraction dynamics in the case of fast transfers. Extractions of uranium, plutonium and neptunium in a laboratory centrifugal extractor

International Nuclear Information System (INIS)

Bergeonneau, Philippe

1978-01-01

The liquid-liquid extraction (also named solvent-based extraction) is a very important technique for the reprocessing of irradiated nuclear fuels. This research thesis is based on the use of a laboratory centrifugal extractor which allows interesting conditions to be achieved: fast transfer due to an intense solution mixing, very short duration of contact between solutions. Thus, after a report of a bibliographical study on chemical mechanisms of extraction, on the composition of extracted species, on extraction kinetics, and on centrifugal extractors, this thesis reports the design, fabrication and use of a centrifugal extractor: presentation of fundamental principles, description and characteristics (materials, hydrodynamic operation test and problems, prototype). It reports studies of fast transfer kinetics: mathematical processing, result interpretation, results and discussions of extraction kinetics for nitric acid, uranium VI and IV, plutonium IV, neptunium IV, and comparison of the different extraction kinetics

On the interaction of uranium with the bioligands citric acid and glucose

International Nuclear Information System (INIS)

Steudtner, Robin

2011-01-01

For a better understanding of the actinide behaviour in human (in term of metabolism, retention, excretion) and in geological and biological systems, it is of prime importance to have a good knowledge of the relevant speciation. In model systems the chemical behaviour of uranium regarding complex formation and redox reaction were investigated. On this basis determinates thermodynamics constants and redox behaviour are used to prognoses a safety assessment for the respective system. The pentavalent uranium(V) is a metastable intermediate in natural redox system between uranium(IV) and uranium(VI). In this study the uranium(V) fluorescence was detected by laser spectroscopic methods (λ ex = 255 nm) for the first time. The peak maxima (λ ex = 255 nm) of luminescence spectrum of the photo reduced U(V) in aqueous perchlorate/2-propanol solution was detected at 440 nm and a fluorescence lifetime of 1.1 ± 0.02 μs was calculated. The stable aqueous uranyl(V)-tricarbonate complex was characterized by fluorescence spectroscopy (λ ex = 255 nm and 408 nm). The known quench effects of carbonate could be minimized by coupling the laser fluorescence system with the low temperature technique. The resulting U(V) fluorescence emission bands were detected between 375 nm and 445 nm. The peak maxima were identified at 401.5 nm (λ ex = 255 nm) and 413.0 nm (λ ex = 408 nm). The fluorescence lifetime of the uranyl(V)-carbonate species was determined at 153 K as 120 ± 0.1 μs (λ ex = 255 nm). In addition the fluorescence of uranium(V) was verifies by confocal laser scanning microscopy. The oxidation process from uranium(IV) to uranium(VI) was investigated on solid uraninite (UO 2 ) and uranium(IV) tetra chloride (UCl 4 ) and a 1 x 10 -2 M uranium(IV) sulphate (U IV SO 4 ) solution. By continuous oxygen transfer the uranium(IV) was oxidized slowly to uranium(VI). The temporal process was studied by the confocal laser scanning microscopy using an excitation wavelength of 408 nm. The

PROCESS OF RECOVERING URANIUM FROM ITS ORES

Science.gov (United States)

Galvanek, P. Jr.

1959-02-24

A process is presented for recovering uranium from its ores. The crushed ore is mixed with 5 to 10% of sulfuric acid and added water to about 5 to 30% of the weight of the ore. This pugged material is cured for 2 to 3 hours at 100 to 110 deg C and then cooled. The cooled mass is nitrate-conditioned by mixing with a solution equivalent to 35 pounds of ammunium nitrate and 300 pounds of water per ton of ore. The resulting pulp containing 70% or more solids is treated by upflow percolation with a 5% solution of tributyl phosphate in kerosene at a rate equivalent to a residence time of about one hour to extract the solubilized uranium. The uranium is recovered from the pregnant organic liquid by counter-current washing with water. The organic extractant may be recycled. The uranium is removed from the water solution by treating with ammonia to precipitate ammonium diuranate. The filtrate from the last step may be recycled for the nitrate-conditioning treatment.

Uranium series disequilibrium measurements at Mol, Belgium

International Nuclear Information System (INIS)

Ivanovich, M.; Wilkins, M.A.

1985-02-01

The contract just completed has funded two parallel uranium series disequilibrium studies and the aims of and the progress to completion of these studies are given in this report. The larger study was concerned with the measurement of uranium series disequilibrium in ground waters derived from sand layers above and below the Boom Clay formation in North East Belgium. The disequilibrium data are analysed in terms of uranium, thorium and radium isotopic geochemistries and in terms of water types and their mixing in the regional groundwater system. It is concluded that most sampled waters are mixtures of younger and older waters. No true old water end-members have been sampled. Simple considerations of the uranium isotopic data indicate that the longest residence times of the sampled waters are not much in excess of 1 to 10 x 10 3 y. Detailed mixing patterns could not be established from this limited data set particularly in the absence of more detailed modelling in conjunction with groundwater hydraulic pressure and flow direction data. (author)

Lead as a pathfinder for uranium mineralization

International Nuclear Information System (INIS)

Shouls, M.M.

1983-01-01

The theoretical aspects of the formation of radiogenic lead anomalies from uranium and thorium mineralization are discussed in the light of differing mobilities of the parent elements and the stable lead daughter. It is concluded that recognizable lead anomalies can persist in the weathered tops of ancient uranium deposits, and such anomalies can be identified from the stable lead isotope ratios. In addition, with mixed U-Th mineralization lead isotopic ratios may be identified after most of the uranium has been leached away. The theoretical models also include possible additions of entrained lead with the mineralization and its effects on the isotopic ratios. This reasoning was tested in the evaluation of a radiometric anomaly in northern Malawi where a discrepancy between the U and eU values suggested a uranium-depleted mixed U-Th deposit. However, the partly coincident lead anomaly did not fit the isotope models proposed in the first part of the paper, and they indicated an unexpectedly young age. The anomaly was therefore downgraded but the adequacy of the theory was not tested. (author)

Ammonium vanadate titrimetric method for determination of micro amount uranium in rock and soil by using vanadate-gold indicator

International Nuclear Information System (INIS)

Li Yucheng.

1990-01-01

A new vanadate-gold indicator was successfully applied to the ammonium vanadate titrimetric method for determination of micro amount uranium in rock and soil. Uranium in 0.1g of sample is reduced by titanium trichloride in phosphoric acid. Excessive Ti (III) and other low-valent ions are oxidized by sodium nitrite, while the complex of uranium (IV)-phosphate is not oxidized. Excessive nitrite is destroyed by urea. When the concentration of phosphoric acid is 22-24 % , adding two drops of vanadate-gold indicator, uranium (IV) is titrated by standardized ammonium vanadate solution (T = 0.02-20gU/ml) and the end-point is judged by a violet-red color appearance

Studies on the determination of uranium by potentiometry

International Nuclear Information System (INIS)

Venkataramana, P.; John, Mary; Nair, P.R.; Kasar, U.M.; Natarajan, P.R.

1981-01-01

A potentiometric method for the determination of uranium standardised earlier has been in use for the chemical quality control of plutonium fuels. The method involves the reduction of U(VI) in phosphoric acid medium and titration of U(IV) against Cr(VI). An extension of the range of the quantity of uranium determined by the same method is reported here. The precisions have been evaluated at 13 concentration levels. 20 titrations were carried out at each concentration. the precision at 20 μg level was found to be 3.8% while it was better than 0.03% at concentrations ranging from 20 mg upto 200 mg. At 100 mg and 200 mg of uranium the total volume of the reagent solutions was 50 ml while in other cases it was 25 ml. The effects of a few impurities on the uranium determination were also studied for the 2-5 mg range of uranium. (author)

Oxidative Uranium Release from Anoxic Sediments under Diffusion-Limited Conditions.

Science.gov (United States)

Bone, Sharon E; Cahill, Melanie R; Jones, Morris E; Fendorf, Scott; Davis, James; Williams, Kenneth H; Bargar, John R

2017-10-03

Uranium (U) contamination occurs as a result of mining and ore processing; often in alluvial aquifers that contain organic-rich, reduced sediments that accumulate tetravalent U, U(IV). Uranium(IV) is sparingly soluble, but may be mobilized upon exposure to nitrate (NO 3 - ) and oxygen (O 2 ), which become elevated in groundwater due to seasonal fluctuations in the water table. The extent to which oxidative U mobilization can occur depends upon the transport properties of the sediments, the rate of U(IV) oxidation, and the availability of inorganic reductants and organic electron donors that consume oxidants. We investigated the processes governing U release upon exposure of reduced sediments to artificial groundwater containing O 2 or NO 3 - under diffusion-limited conditions. Little U was mobilized during the 85-day reaction, despite rapid diffusion of groundwater within the sediments and the presence of nonuraninite U(IV) species. The production of ferrous iron and sulfide in conjunction with rapid oxidant consumption suggested that the sediments harbored large concentrations of bioavailable organic carbon that fueled anaerobic microbial respiration and stabilized U(IV). Our results suggest that seasonal influxes of O 2 and NO 3 - may cause only localized mobilization of U without leading to export of U from the reducing sediments when ample organic carbon is present.

Spectrochemical method of uranium determination in sea water

International Nuclear Information System (INIS)

Koval'chuk, L.I.; Koryukova, V.P.; Andrianov, A.M.

1979-01-01

A spectrochemical method of uranium determination in sea water is reported. The method involves the use of hydrated titanium oxide as a concentrator and a substrate for the analysis. The uranium-containing concentrate mixed with carbon powder (1:1) is burned in the alternating current ark (i=15 A) and the spectra are recorded by a diffraction spectrometer. The analytical line of uranium is 2865.14 A. The variation coefficient is 12%

Late-occurring pulmonary pathologies following inhalation of mixed oxide (uranium + plutonium oxide) aerosol in the rat.

Science.gov (United States)

Griffiths, N M; Van der Meeren, A; Fritsch, P; Abram, M-C; Bernaudin, J-F; Poncy, J L

2010-09-01

Accidental exposure by inhalation to alpha-emitting particles from mixed oxide (MOX: uranium and plutonium oxide) fuels is a potential long-term health risk to workers in nuclear fuel fabrication plants. For MOX fuels, the risk of lung cancer development may be different from that assigned to individual components (plutonium, uranium) given different physico-chemical characteristics. The objective of this study was to investigate late effects in rat lungs following inhalation of MOX aerosols of similar particle size containing 2.5 or 7.1% plutonium. Conscious rats were exposed to MOX aerosols and kept for their entire lifespan. Different initial lung burdens (ILBs) were obtained using different amounts of MOX. Lung total alpha activity was determined by external counting and at autopsy for total lung dose calculation. Fixed lung tissue was used for anatomopathological, autoradiographical, and immunohistochemical analyses. Inhalation of MOX at ILBs ranging from 1-20 kBq resulted in lung pathologies (90% of rats) including fibrosis (70%) and malignant lung tumors (45%). High ILBs (4-20 kBq) resulted in reduced survival time (N = 102; p inhalation result in similar risk for development of lung tumors as compared with industrial plutonium oxide.

Impact of receipt of coprocessed uranium/plutonium on advanced accountability concepts and fabrication facilities. Addendum 1 to application of advanced accountability concepts in mixed oxide fabrication

International Nuclear Information System (INIS)

Bastin, J.J.; Jump, M.J.; Lange, R.A.; Randall, C.C.

1977-11-01

The Phase I study of the application of advanced accountability methods (DYMAC) in a uranium/plutonium mixed oxide facility was extended to assess the effect of coprocessed UO 2 --PuO 2 feed on the observations made in the original Phase I effort and on the proposed Phase II program. The retention of plutonium mixed with uranium throughout the process was also considered. This addendum reports that coprocessed feed would have minimal effect on the DYMAC program, except in the areas of material specifications, starting material delivery schedule, and labor requirements. Each of these areas is addressed, as are the impact of coprocessed feed at a large fuel fabrication facility and the changes needed in the dirty scrap recovery process to maintain the lower plutonium levels which may be required by future nonproliferation philosophy. An amended schedule for Phase II is included

Thermal diffusivity and conductivity of thorium- uranium mixed oxides

Science.gov (United States)

Saoudi, M.; Staicu, D.; Mouris, J.; Bergeron, A.; Hamilton, H.; Naji, M.; Freis, D.; Cologna, M.

2018-03-01

Thorium-uranium oxide pellets with high densities were prepared at the Canadian Nuclear Laboratories (CNL) by co-milling, pressing, and sintering at 2023 K, with UO2 mass contents of 0, 1.5, 3, 8, 13, 30, 60 and 100%. At the Joint Research Centre, Karlsruhe (JRC-Karlsruhe), thorium-uranium oxide pellets were prepared using the spark plasma sintering (SPS) technique with 79 and 93 wt. % UO2. The thermal diffusivity of (Th1-xUx)O2 (0 ≤ x ≤ 1) was measured at CNL and at JRC-Karlsruhe using the laser flash technique. ThO2 and (Th,U)O2 with 1.5, 3, 8 and 13 wt. % UO2 were found to be semi-transparent to the infrared wavelength of the laser and were coated with graphite for the thermal diffusivity measurements. This semi-transparency decreased with the addition of UO2 and was lost at about 30 wt. % of UO2 in ThO2. The thermal conductivity was deduced using the measured density and literature data for the specific heat capacity. The thermal conductivity for ThO2 is significantly higher than for UO2. The thermal conductivity of (Th,U)O2 decreases rapidly with increasing UO2 content, and for UO2 contents of 60% and higher, the conductivity of the thorium-uranium oxide fuel is close to UO2. As the mass difference between the Th and U atoms is small, the thermal conductivity decrease is attributed to the phonon scattering enhanced by lattice strain due to the introduction of uranium in ThO2 lattice. The new results were compared to the data available in the literature and were evaluated using the classical phonon transport model for oxide systems.

Determining uranium speciation in contaminated soils by molecular spectroscopic methods: Examples from the Uranium in Soils Integrated Demonstration

International Nuclear Information System (INIS)

Allen, P.G.; Berg, J.M.; Chisholm-Brause, C.J.; Conradson, S.D.; Donohoe, R.J.; Morris, D.E.; Musgrave, J.A.; Tait, C.D.

1994-01-01

The US Department of Energy's former uranium production facility located at Fernald, OH (18 mi NW of Cincinnati) is the host site for an Integrated Demonstration for remediation of uranium-contaminated soils. A wide variety of source terms for uranium contamination have been identified reflecting the diversity of operations at the facility. Most of the uranium contamination is contained in the top ∼1/2 m of soil, but uranium has been found in perched waters indicating substantial migration. In support of the development of remediation technologies and risk assessment, we are conducting uranium speciation studies on untreated and treated soils using molecular spectroscopies. Untreated soils from five discrete sites have been analyzed. We have found that ∼80--90% of the uranium exists as hexavalent UO 2 2+ species even though many source terms consisted of tetravalent uranium species such as UO 2 . Much of the uranium exists as microcrystalline precipitates (secondary minerals). There is also clear evidence for variations in uranium species from the microscopic to the macroscopic scale. However, similarities in speciation at sites having different source terms suggest that soil and groundwater chemistry may be as important as source term in defining the uranium speciation in these soils. Characterization of treated soils has focused on materials from two sites that have undergone leaching using conventional extractants (e.g., carbonate, citrate) or novel chelators such as Tiron. Redox reagents have also been used to facilitate the leaching process. Three different classes of treated soils have been identified based on the speciation of uranium remaining in the soils. In general, the effective treatments decrease the total uranium while increasing the ratio of U(IV) to U(VI) species

Thermal conductivity of beginning-of-life uranium-plutonium mixed oxide fuel for fast reactor (Interim report)

International Nuclear Information System (INIS)

Inoue, Masaki; Mizuno, Tomoyasu; Asaga, Takeo

1997-11-01

Thermal conductivity of uranium-plutonium mixed oxide fuel for fast reactor at beginning-of-life was correlated based on the recent results in order to apply to the fuel design and the fuel performance analysis. A number of experimental results of unirradiated fuel specimens were corrected from open literatures and PNC internal reports and examined for the database. In this work two porosity correction factors were needed for high density fuel and low density fuel (around the current Monju specification). The universal porosity correction factor was not determined in this work. In the next step, theoretical and analytical considerations should be taken into account. (J.P.N.)

Uranium and thorium based phosphate matrix: synthesis, characterizations and lixiviation; Matrices a base de phosphate d'uranium et de thorium: syntheses, caracterisations et lixiviation

Energy Technology Data Exchange (ETDEWEB)

Dacheux, N

1995-03-01

In the framework of the search for a ceramic material usable in the radioactive waste storage, uranium and thorium phosphates have been investigated. Their experimental synthesis conditions have been entirely reviewed, they lead to the preparation of four new compounds: U(UO{sub 2})(PO{sub 4}){sub 2}, U{sub 2}O(PO{sub 4}){sub 2}, UCIPO{sub 4}, 4H{sub 2}O, and Th{sub 4}(PO{sub 4}){sub 4}P{sub 2}O{sub 7}. Experimental evidenced are advanced for non existent compounds such as: U{sub 3}(PO{sub 4}){sub 4}, U{sub 2}O{sub 3}P{sub 2}O{sub 7} and Th{sub 3} (PO{sub 4}){sub 4}. Characterization by several techniques (X-rays and neutron powder diffractions, UV-Visible and Infra-red spectroscopies, XPS,...) were performed. The ab initio structure determination of U(UO{sub 2})(PO{sub 4}){sub 2} has been achieved by X-rays and refined by neutron diffractions. Through its physico-chemical analysis, we found that this compound was a new mixed valence uranium phosphate in which U{sup 4+} and UO{sub 2}{sup 2+} ions are ordered in pairs along parallel chains according to a new type of arrangement. Reaction mechanism, starting from UCIPO{sub 4}, 4H{sub 2}O and based on redox processes of uranium in solid state was set up. From two main matrices U(UO{sub 2})(PO{sub 4}){sub 2} and Th{sub 4}(PO{sub 4}){sub 4}P{sub 2}O{sub 7}, solid solutions were studied. They consist of replacement of U(IV) by Th(IV) and reversely. The leaching tests on pure, loaded and doped matrices were performed in terms of storage time, pH of solutions, and determined by the use of solids labelled with {sup 230}U or by the measurement of uranyl concentration by Laser-Induced Time-Resolved Spectro-fluorimetry. Average concentration of uranium in the liquid phase is around 10{sup -4} M to 10{sup -6} M. Taking into account the very low solubilities of the studied phosphate ceramics, we estimated their chemical performances promising as an answer to the important nuclear waste problem, if we compare them to the glasses

Method of precipitating uranium from an aqueous solution and/or sediment

Science.gov (United States)

Tokunaga, Tetsu K; Kim, Yongman; Wan, Jiamin

2013-08-20

A method for precipitating uranium from an aqueous solution and/or sediment comprising uranium and/or vanadium is presented. The method includes precipitating uranium as a uranyl vanadate through mixing an aqueous solution and/or sediment comprising uranium and/or vanadium and a solution comprising a monovalent or divalent cation to form the corresponding cation uranyl vanadate precipitate. The method also provides a pathway for extraction of uranium and vanadium from an aqueous solution and/or sediment.

Synthesis and reduction of uranium(V) imido complexes with redox-active substituents

Energy Technology Data Exchange (ETDEWEB)

Mullane, Kimberly C.; Carroll, Patrick J.; Schelter, Eric J. [P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, PA (United States)

2017-04-27

Organic azides that contain naphthyl functional groups were used to prepare uranium(V) imido complexes U{sup V}[=NC(2-naph)Ph{sub 2}][N(SiMe{sub 3}){sub 2}]{sub 3} (2), U{sup V}[=NC(2-naph){sub 3}][N(SiMe{sub 3}){sub 2}]{sub 3} (3), and U{sup V}[=N(2-naph)][N(SiMe{sub 3}){sub 2}]{sub 3} (4), and their properties were compared with U{sup V}[=NCPh{sub 3}][N(SiMe{sub 3}){sub 2}]{sub 3} (1). The electronic structures of these compounds were investigated by solution electrochemistry studies, which revealed accessible U{sup V/VI}, U{sup IV/V}, and naphthalene{sup 0}/naphthalene{sup -1} couples. The uranium(V) naphthylimido complexes were reduced by potassium graphite to yield their uranium(IV) congeners K[U{sup IV}[=NC(2-naph)Ph{sub 2}][N(SiMe{sub 3}){sub 2}]{sub 3}] (2-K), K[U{sup IV}[=NC(2-naph){sub 3}][N(SiMe{sub 3}){sub 2}]{sub 3}] (3-K), and K[U{sup IV}[=N(2-naph)][N(SiMe{sub 3}){sub 2}]{sub 3}] (4-K). The electronic structure of the dianionic compounds were investigated by DFT calculations, and this revealed that the second reduction was ligand-based, which opens the possibility of accomplishing multi-electron redox chemistry by using a tailored multiply-bonded ligand. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Extraction of uranium from seawater: evaluation of uranium resources and plant siting

International Nuclear Information System (INIS)

Rodman, M.R.; Gordon, L.I.; Chen, A.C.T.

1979-02-01

This report deals with the evaluation of U.S. coastal waters as a uranium resource and with the selection of a suitable site for construction of a large-scale plant for uranium extraction. Evaluation of the resource revealed that although the concentration of uranium is quite low, about 3.3 ppB in seawater of average oceanic salinity, the amount present in the total volume of the oceans is very great, some 4.5 billion metric tons. Of this, perhaps only that uranium contained in the upper 100 meters or so of the surface well-mixed layer should be considered accessible for recovery, some 160 million tonnes. The study indicated that open ocean seawater acquired for the purpose of uranium extraction would be a more favorable resource than rivers entering the sea, cooling water of power plants, or the feed or effluent streams of existing plants producing other products such as magnesium, bromine, or potable and/or agricultural water from seawater. Various considerations led to the selection of a site for a pumped seawater coastal plant at a coastal location. Puerto Yabucoa, Puerto Rico was selected. Recommendations are given for further studies. 21 figures, 8 tables

Extraction of uranium from seawater: evaluation of uranium resources and plant siting

Energy Technology Data Exchange (ETDEWEB)

Rodman, M.R.; Gordon, L.I.; Chen, A.C.T.

1979-02-01

This report deals with the evaluation of U.S. coastal waters as a uranium resource and with the selection of a suitable site for construction of a large-scale plant for uranium extraction. Evaluation of the resource revealed that although the concentration of uranium is quite low, about 3.3 ppB in seawater of average oceanic salinity, the amount present in the total volume of the oceans is very great, some 4.5 billion metric tons. Of this, perhaps only that uranium contained in the upper 100 meters or so of the surface well-mixed layer should be considered accessible for recovery, some 160 million tonnes. The study indicated that open ocean seawater acquired for the purpose of uranium extraction would be a more favorable resource than rivers entering the sea, cooling water of power plants, or the feed or effluent streams of existing plants producing other products such as magnesium, bromine, or potable and/or agricultural water from seawater. Various considerations led to the selection of a site for a pumped seawater coastal plant at a coastal location. Puerto Yabucoa, Puerto Rico was selected. Recommendations are given for further studies. 21 figures, 8 tables.

Remediation of soil/concrete contaminated with uranium and radium by biological method

International Nuclear Information System (INIS)

Gye-Nam Kim; Seung-Su Kim; Hye-Min Park; Won-Suk Kim; Uk-Ryang Park; Jei-Kwon Moon

2013-01-01

Biological method was studied for remediation of soil/concrete contaminated with uranium and radium. Optimum experiment conditions for mixing ratios of penatron and soil, and the pH of soil was obtained through several bioremediations with soil contaminated with uranium and radium. It was found that an optimum mixing ratio of penatron for bioremediation of uranium soil was 1 %. Also, the optimum pH condition for bioremediation of soil contaminated with uranium and radium was 7.5. The removal efficiencies of uranium and radium from higher concentration of soil were rather reduced in comparison with those from lower concentration of soil. Meanwhile, the removal of uranium and radium in concrete by bioremediation is possible but the removal rate from concrete was slower than that from soil. The removal efficiencies of uranium and radium from soil under injection of 1 % penatron at pH 7.5 for 120 days were 81.2 and 81.6 %, respectively, and the removal efficiencies of uranium and radium from concrete under the same condition were 63.0 and 45.2 %, respectively. Beyond 30 days, removal rates of uranium and radium from soil and concrete by bioremediation was very slow. (author)

Depleted uranium hexafluoride: Waste or resource?

International Nuclear Information System (INIS)

Schwertz, N.; Zoller, J.; Rosen, R.; Patton, S.; Bradley, C.; Murray, A.

1995-07-01

The US Department of Energy is evaluating technologies for the storage, disposal, or re-use of depleted uranium hexafluoride (UF 6 ). This paper discusses the following options, and provides a technology assessment for each one: (1) conversion to UO 2 for use as mixed oxide duel, (2) conversion to UO 2 to make DUCRETE for a multi-purpose storage container, (3) conversion to depleted uranium metal for use as shielding, (4) conversion to uranium carbide for use as high-temperature gas-cooled reactor (HTGR) fuel. In addition, conversion to U 3 O 8 as an option for long-term storage is discussed

(NH4)[V1-xIIIVxIV(AsO4)F1-xOx]: A new mixed valence vanadium(III,IV) fluoro-arsenate with ferromagnetic interactions and electronic conductivity

International Nuclear Information System (INIS)

Berrocal, Teresa; Mesa, Jose L.; Pizarro, Jose L.; Bazan, Begona; Ruiz de Larramendi, Idoia; Arriortua, Maria I.; Rojo, Teofilo

2009-01-01

A new mixed valence vanadium(III,IV) fluoro-arsenate compound, with formula (NH 4 )[V 1-x III V x IV (AsO 4 )F 1-x O x ] and KTP structure-type, has been synthesized by mild hydrothermal techniques. The crystal structure has been solved from single crystal X-ray diffraction data in the Pna2 1 orthorhombic space group. The unit-cell parameters are a=13.196(2) A, b=6.628(1) A and c=10.7379(7) A with Z=8. The final R factors were R1=0.0438 and wR2=0.0943 [all data]. The crystal structure consists of a three-dimensional framework formed by (V III,IV O 4 F 2 ) octahedra and (AsO 4 ) 3- tetrahedra arsenate oxoanions. The vanadium(III,IV) cations, from the (V III,IV O 4 F 2 ) octahedra, are linked through the fluorine atoms giving rise to zigzag chains. The ammonium cations are located in the cavities of the structure compensating the anionic charge of the [V 1-x III V x IV (AsO 4 )F 1-x O x ] - inorganic skeleton. The thermal stability limit of the phase is 345 deg. C, around to this temperature the ammonium cation and fluoride anion are lost. The IR spectrum shows the characteristic bands of the (NH 4 ) + and (AsO 4 ) 3- ions. Magnetic measurements indicate the existence of weak ferromagnetic interactions. Electronic conductivity, via a hopping mechanism, occurs with an activation energy of 0.66 eV. - Graphical abstract: Polyhedral view of the crystal structure of (NH 4 )[V III 1-x V IV x (AsO 4 )F 1-x O x

Reduction of uranium in disposal conditions of spent nuclear fuel

International Nuclear Information System (INIS)

Myllykylae, E.

2008-02-01

This literature study is a summary of publications, in which the reduction of uranium by iron has been investigated in anaerobic groundwater conditions or in aqueous solution in general. The basics of the reduction phenomena and the oxidation states, complexes and solubilities of uranium and iron in groundwaters are discussed as an introduction to the subject, as well as, the Finnish disposal concept of spent nuclear fuel. The spent fuel itself mainly (∼96 %) consists of a sparingly soluble uranium(IV) dioxide, UO 2 (s), which is stable phase in the anticipated reducing disposal conditions. If spent fuel gets in contact with groundwater, oxidizing conditions might be induced by the radiolysis of water, or by the intrusion of oxidizing glacial melting water. Under these conditions, the oxidation and dissolution of uranium dioxide to more soluble U(VI) species could occur. This could lead to the mobilization of uranium and other components of spent fuel matrix including fission products and transuranium elements. The reduction of uranium back to oxidation state U(IV) can be considered as a favourable immobilization mechanism in a long-term, leading to precipitation due to the low solubility of U(IV) species. The cast iron insert of the disposal canister and its anaerobic corrosion products are the most important reductants under disposal conditions, but dissolved ferrous iron may also function as reductant. Other iron sources in the buffer or near-field rock, are also considered as possible reductants. The reduction of uranium is a very challenging phenomenon to investigate. The experimental studies need e.g. well-controlled anoxic conditions and measurements of oxidation states. Reduction and other simultaneous phenomena are difficult to distinghuish. The groundwater conditions (pH, Eh and ions) influence on the prevailing complexes of U and Fe and on forming corrosion products of iron and, thus they determine also the redox chemistry. The partial reduction of

Uranium speciation in 30-year old Freital mine tailings: an EXAFS, {mu}-XRD, and {mu}-XRF study

Energy Technology Data Exchange (ETDEWEB)

Scheinost, A.C.; Hennig, C. [Institute of Radiochemistry, FZR, D-01314 Dresden (Germany); Somogyi, A. [Synchrotron Soleil, F-91192 Gif-sur-Yvette (France); Martinez-Criado, G. [ESRF, ID-22, F-38043 Grenoble (France); Knappik, R. [VKTA Rossendorf, D-01314 Dresden (Germany)

2005-07-01

Full text of publication follows: Risk assessments of actinide-contaminated soils and sediments require detailed knowledge of actinide speciation and its long-term kinetics. Former Saxonian mine tailings, which have been covered but else left undisturbed, are ideally suited to study changes in uranium speciation over timescales of decades. We investigated the major uranium species in two samples from buried mine tailings using a combination of Synchrotron-based microfocus-techniques ({mu}-XRF, {mu}-XRD with micrometer resolution), bulk EXAFS spectroscopy, and chemical extractions. In sample F1 (5 m depth, oxic, pH 8, U = 440 mg/kg, high Ca, S, Pb, Cu, Zn concentrations), uranium is diffusely distributed among aggregates of layer silicates (muscovite, illite and kaolinite). The chemical extractions and EXAFS results confirm that uranium is sorbed to these minerals, but is not incorporated into their crystal structure. Sorption is also in line with the high pH and low carbonate concentrations in pore water. In sample F3 (12 m depth, oxic, pH 4, U = 430 mg/kg), the combination of {mu}-XRF and {mu}-XRD enabled us to identify several U(IV) and U(VI) containing minerals like coffinite, uraninite, uranyl hydroxide, and vanuralite. Only a minor part of U is sorbed to layer silicates as confirmed by chemical extractions and EXAFS spectroscopy. At smaller depth (F1, 5 m), sulfuric acid from the ore extraction procedure was completely neutralized by the construction waste used as cover material, resulting in precipitation of jarosite and gypsum. Even 30 years after the ore extraction, uranium remains highly soluble. At greater depth (F3, 12 m), the low pH from ore extraction was conserved. The presence of U(IV) minerals suggest either precipitation of secondary (IV) minerals due to microbial redox activity, or incomplete dissolution of primary (IV) minerals due to ore processing inefficiency of these older sediments. The U(IV) minerals were recalcitrant during chemical

Uranium speciation in 30-year old Freital mine tailings: an EXAFS, μ-XRD, and μ-XRF study

International Nuclear Information System (INIS)

Scheinost, A.C.; Hennig, C.; Somogyi, A.; Martinez-Criado, G.; Knappik, R.

2005-01-01

Full text of publication follows: Risk assessments of actinide-contaminated soils and sediments require detailed knowledge of actinide speciation and its long-term kinetics. Former Saxonian mine tailings, which have been covered but else left undisturbed, are ideally suited to study changes in uranium speciation over timescales of decades. We investigated the major uranium species in two samples from buried mine tailings using a combination of Synchrotron-based microfocus-techniques (μ-XRF, μ-XRD with micrometer resolution), bulk EXAFS spectroscopy, and chemical extractions. In sample F1 (5 m depth, oxic, pH 8, U = 440 mg/kg, high Ca, S, Pb, Cu, Zn concentrations), uranium is diffusely distributed among aggregates of layer silicates (muscovite, illite and kaolinite). The chemical extractions and EXAFS results confirm that uranium is sorbed to these minerals, but is not incorporated into their crystal structure. Sorption is also in line with the high pH and low carbonate concentrations in pore water. In sample F3 (12 m depth, oxic, pH 4, U = 430 mg/kg), the combination of μ-XRF and μ-XRD enabled us to identify several U(IV) and U(VI) containing minerals like coffinite, uraninite, uranyl hydroxide, and vanuralite. Only a minor part of U is sorbed to layer silicates as confirmed by chemical extractions and EXAFS spectroscopy. At smaller depth (F1, 5 m), sulfuric acid from the ore extraction procedure was completely neutralized by the construction waste used as cover material, resulting in precipitation of jarosite and gypsum. Even 30 years after the ore extraction, uranium remains highly soluble. At greater depth (F3, 12 m), the low pH from ore extraction was conserved. The presence of U(IV) minerals suggest either precipitation of secondary (IV) minerals due to microbial redox activity, or incomplete dissolution of primary (IV) minerals due to ore processing inefficiency of these older sediments. The U(IV) minerals were recalcitrant during chemical extractions

Fabrication of uranium-plutonium mixed nitride fuel pins (88F-5A) for first irradiation test at JMTR

International Nuclear Information System (INIS)

Suzuki, Yasufumi; Iwai, Takashi; Arai, Yasuo; Sasayama, Tatsuo; Shiozawa, Ken-ichi; Ohmichi, Toshihiko; Handa, Muneo

1990-07-01

A couple of uranium-plutonium mixed nitride fuel pins was fabricated for the first irradiation tests at JMTR for the purpose of understanding the irradiation behavior and establishing the feasibility of nitride fuels as advanced FBR fuels. The one of the pins was fitted with thermocouples in order to observe the central fuel temperature. In this report, the fabrication procedure of the pins such as pin design, fuel pellet fabrication and characterizations, welding of fuel pins, and inspection of pins are described, together with the outline of the new TIG welder installed recently. (author)

Spectroscopic Evidence of Uranium Immobilization in Acidic ...

Science.gov (United States)

Biogeochemistry of uranium in wetlands plays important roles in U immobilization in storage ponds of U mining and processing facilities but has not been well understood. The objective of this work was to study molecular mechanisms responsible for high U retention by Savannah River Site (SRS) wetland sediments under varying redox and acidic (pH = 2.6-5.8) conditions using U L3-edge X-ray absorption spectroscopy. Uranium in the SRS wetland sediments existed primarily as U(VI) bonded as a bidentate to carboxylic sites (U-C bond distance at ~2.88 Å), rather than phenolic or other sites of natural organic matter (NOM). In microcosms simulating the SRS wetland process, U immobilization on roots was 2 orders of magnitude higher than on the adjacent brown or more distant white sands in which U was U(VI). Uranium on the roots were both U(IV) and U(VI), which were bonded as a bidentate to carbon, but the U(VI) may also form a U phosphate mineral. After 140 days of air exposure, all U(IV) was reoxidized to U(VI) but remained as a bidentate bonding to carbon. This study demonstrated NOM and plant roots can highly immobilize U(VI) in the SRS acidic sediments, which has significant implication on the long-term stewardship of U-contaminated wetlands. There were several former U processing facilities at the Savannah River Site (SRS), Aiken, SC. As a result of their operations, uranium has entered the surrounding environments. For example, approximately 45,000 kg o

Airborne effluent control at uranium mills

International Nuclear Information System (INIS)

Sears, M.B.

1976-01-01

The Oak Ridge National Laboratory has made an engineering cost--environmental benefit study of radioactive waste treatment systems for decreasing the amount of radioactive materials released from uranium ore processing mills. This paper summarizes the results of the study which pertain to the control and/or abatement of airborne radioactive materials from the mill processes. The tailings area is not included. Present practices in the uranium milling industry, with particular emphasis on effluent control and waste management, have been surveyed. A questionnaire was distributed to each active mill in the United States. Replies were received from about 75 percent of the mill operators. Visits were made to six operating uranium mills that were selected because they represented the different processes in use today and the newest, most modern in mill designs. Discussions were held with members of the Region IV Office of NRC and the Grand Junction Office of ERDA. Nuclear Science Abstracts, as well as other sources, were searched for literature pertinent to uranium mill processes, effluent control, and waste management

Initial process development for uranium bioprecipitation

International Nuclear Information System (INIS)

Truex, M.; Peyton, B.; Gorby, Y.; Valentine, N.

1994-01-01

Some bacteria can destabilize soluble metal complexes by enzymatically reducing the metal to a valence state where insoluble compounds are formed. For instance, oxidized uranium (VI) is highly soluble, but it precipitates from solution as the U(IV) oxide uraninite after microbial reduction. The advantage of this technology is that the uranium is easily separated from the aqueous phase, resulting in a small volume of relatively pure uraninite waste. A dissimilatory iron-reducing bacterium capable of uranium reduction was found to have a maximum growth rate of 0.142/hr, a Monod half-saturation constant of 3.4 mg/L, and a cellular yield of 0.071 mg-biomass/mg-iron for iron reduction at 30 C and pH 6.8. The kinetics of iron reduction were used to predict the performance of several reactor configurations for reduction of metals of interest such as uranium. A stirred-tank reactor in series with a plug-flow reactor was determined to be the best configuration for application of the bioprecipitation technology in a continuous-flow process

On line spectrophotometry with optical fibers. Application to uranium-plutonium separation in a spent fuel reprocessing plant

International Nuclear Information System (INIS)

Boisde, G.; Mus, G.; Tachon, M.

1985-06-01

Optimization of mixer-settler operation for uranium-plutonium separation in the Purex process can be obtained by remote spectrophotometry with optical fibers. Data acquisition on uranium VI, uranium IV and plutonium III is examined in function of acidity and nitrate content of the solution. Principles for on line multicomponent monitoring and mathematical modelization of the measurements are described [fr

Theoretical modeling of the uranium 4f XPS for U(VI) and U(IV) oxides

Energy Technology Data Exchange (ETDEWEB)

Bagus, Paul S. [Department of Chemistry, University of North Texas, Denton, Texas 76203-5017 (United States); Nelin, Connie J. [Consulting and Services, 6008 Maury' s Trail, Austin, Texas 78730 (United States); Ilton, Eugene S. [Pacific Northwest National Laboratory, Richland, Washington 99352 (United States)

2013-12-28

A rigorous study is presented of the physical processes related to X-Ray photoelectron spectroscopy, XPS, in the 4f level of U oxides, which, as well as being of physical interest in themselves, are representative of XPS in heavy metal oxides. In particular, we present compelling evidence for a new view of the screening of core-holes that extends prior understandings. Our analysis of the screening focuses on the covalent mixing of high lying U and O orbitals as opposed to the, more common, use of orbitals that are nominally pure U or pure O. It is shown that this covalent mixing is quite different for the initial and final, core-hole, configurations and that this difference is directly related to the XPS satellite intensity. Furthermore, we show that the high-lying U d orbitals as well as the U(5f) orbital may both contribute to the core-hole screening, in contrast with previous work that has only considered screening through the U(5f) shell. The role of modifying the U-O interaction by changing the U-O distance has been investigated and an unexpected correlation between U-O distance and XPS satellite intensity has been discovered. The role of flourite and octahedral crystal structures for U(IV) oxides has been examined and relationships established between XPS features and the covalent interactions in the different structures. The physical views of XPS satellites as arising from shake processes or as arising from ligand to metal charge transfers are contrasted; our analysis provides strong support that shake processes give a more fundamental physical understanding than charge transfer. Our theoretical studies are based on rigorous, strictly ab initio determinations of the electronic structure of embedded cluster models of U oxides with formal U(VI) and U(IV) oxidation states. Our results provide a foundation that makes it possible to establish quantitative relationships between features of the XPS spectra and materials properties.

Theoretical modeling of the uranium 4f XPS for U(VI) and U(IV) oxides

Science.gov (United States)

Bagus, Paul S.; Nelin, Connie J.; Ilton, Eugene S.

2013-12-01

A rigorous study is presented of the physical processes related to X-Ray photoelectron spectroscopy, XPS, in the 4f level of U oxides, which, as well as being of physical interest in themselves, are representative of XPS in heavy metal oxides. In particular, we present compelling evidence for a new view of the screening of core-holes that extends prior understandings. Our analysis of the screening focuses on the covalent mixing of high lying U and O orbitals as opposed to the, more common, use of orbitals that are nominally pure U or pure O. It is shown that this covalent mixing is quite different for the initial and final, core-hole, configurations and that this difference is directly related to the XPS satellite intensity. Furthermore, we show that the high-lying U d orbitals as well as the U(5f) orbital may both contribute to the core-hole screening, in contrast with previous work that has only considered screening through the U(5f) shell. The role of modifying the U-O interaction by changing the U-O distance has been investigated and an unexpected correlation between U-O distance and XPS satellite intensity has been discovered. The role of flourite and octahedral crystal structures for U(IV) oxides has been examined and relationships established between XPS features and the covalent interactions in the different structures. The physical views of XPS satellites as arising from shake processes or as arising from ligand to metal charge transfers are contrasted; our analysis provides strong support that shake processes give a more fundamental physical understanding than charge transfer. Our theoretical studies are based on rigorous, strictly ab initio determinations of the electronic structure of embedded cluster models of U oxides with formal U(VI) and U(IV) oxidation states. Our results provide a foundation that makes it possible to establish quantitative relationships between features of the XPS spectra and materials properties.

Uranium band types in carbonaceous sediments with different diagenesis levels

International Nuclear Information System (INIS)

Borstel, D. von.

1984-01-01

Uraniferous peats, lignites and coals were studied by chemical and geological methods in order to determine the influence of carbonaceous substances with different diagenesis levels on uranium enrichment in sediments. It was found that the main factor of deposit genesis is not the chemical bending of uranium to the organic substance but rather the reduction from mobile U(VI) to immobile U(IV) in the course of diagenesis to epigenesis. (orig./PW) [de

Uranium and thorium based phosphate matrix: synthesis, characterizations and lixiviation; Matrices a base de phosphate d'uranium et de thorium: syntheses, caracterisations et lixiviation

Energy Technology Data Exchange (ETDEWEB)

Dacheux, N

1995-03-01

In the framework of the search for a ceramic material usable in the radioactive waste storage, uranium and thorium phosphates have been investigated. Their experimental synthesis conditions have been entirely reviewed, they lead to the preparation of four new compounds: U(UO{sub 2})(PO{sub 4}){sub 2}, U{sub 2}O(PO{sub 4}){sub 2}, UCIPO{sub 4}, 4H{sub 2}O, and Th{sub 4}(PO{sub 4}){sub 4}P{sub 2}O{sub 7}. Experimental evidenced are advanced for non existent compounds such as: U{sub 3}(PO{sub 4}){sub 4}, U{sub 2}O{sub 3}P{sub 2}O{sub 7} and Th{sub 3} (PO{sub 4}){sub 4}. Characterization by several techniques (X-rays and neutron powder diffractions, UV-Visible and Infra-red spectroscopies, XPS,...) were performed. The ab initio structure determination of U(UO{sub 2})(PO{sub 4}){sub 2} has been achieved by X-rays and refined by neutron diffractions. Through its physico-chemical analysis, we found that this compound was a new mixed valence uranium phosphate in which U{sup 4+} and UO{sub 2}{sup 2+} ions are ordered in pairs along parallel chains according to a new type of arrangement. Reaction mechanism, starting from UCIPO{sub 4}, 4H{sub 2}O and based on redox processes of uranium in solid state was set up. From two main matrices U(UO{sub 2})(PO{sub 4}){sub 2} and Th{sub 4}(PO{sub 4}){sub 4}P{sub 2}O{sub 7}, solid solutions were studied. They consist of replacement of U(IV) by Th(IV) and reversely. The leaching tests on pure, loaded and doped matrices were performed in terms of storage time, pH of solutions, and determined by the use of solids labelled with {sup 230}U or by the measurement of uranyl concentration by Laser-Induced Time-Resolved Spectro-fluorimetry. Average concentration of uranium in the liquid phase is around 10{sup -4} M to 10{sup -6} M. Taking into account the very low solubilities of the studied phosphate ceramics, we estimated their chemical performances promising as an answer to the important nuclear waste problem, if we compare them to the glasses

Uranium uptake of Vetiveria zizanioides (L.) Nash

International Nuclear Information System (INIS)

Luu Viet Hung; Maslov, O.D.; Trinh Thi Thu My; Phung Khac Nam Ho; Dang Duc Nhan

2010-01-01

Uranium uptake of vetiver grass (Vetiveria zizanioides (L.) Nash) from Eutric Fluvisols (AK), Albic Acrisols (BG), Dystric Fluvisols (HP) and Ferralic Acrisols (TC) in northern Vietnam is assessed. The soils were mixed with aqueous solution of uranyl nitrate to make soils contaminated with uranium at 0, 50, 100, 250 mg/kg before planting the grass. The efficiency of uranium uptake by the grass was assessed based on the soil-to-plant transfer factor (TF U , kg·kg -1 ). It was found that the TF U values are dependent upon the soils properties. CEC facilitates the uptake and the increased soil pH could reduce the uptake and translocation of uranium in the plant. Organic matter content, as well as iron and potassium, inhibits the uranium uptake of the grass. It was revealed that the lower fertile soil, the higher uranium uptake. The translocation of uranium in root for all the soil types studied is almost higher than that in its shoot. It seems that vetiver grass could potentially be used for the purpose of phytoremediation of soils contaminated with uranium

Characterization of uranium- and plutonium-contaminated soils by electron microscopy

International Nuclear Information System (INIS)

Buck, E.C.; Dietz, N.L.; Fortner, J.A.; Bates, J.K.; Brown, N.R.

1995-01-01

Electron beam techniques have been used to characterize uranium-contaminated soils from the Fernald Site in Ohio, and also plutonium-bearing 'hot particles, from Johnston Island in the Pacific Ocean. By examining Fernald samples that had undergone chemical leaching it was possible to observe the effect the treatment had on specific uranium-bearing phases. The technique of Heap leaching, using carbonate solution, was found to be the most successful in removing uranium from Fernald soils, the Heap process allows aeration, which facilitates the oxidation of uraninite. However, another refractory uranium(IV) phase, uranium metaphosphate, was not removed or affected by any soil-washing process. Examination of ''hot particles'' from Johnston Island revealed that plutonium and uranium were present in 50--200 nm particles, both amorphous and crystalline, within a partially amorphous aluminum oxide matrix. The aluminum oxide is believed to have undergone a crystalline-to-amorphous transition caused by alpha-particle bombardment during the decay of the plutonium

Reoxidation of Bioreduced Uranium Under Reducing Conditions

International Nuclear Information System (INIS)

Wan, Jiamin; Tokunaga, Tetsu K.; Brodie, Eoin; Wang, Zheming; Zheng, Zuoping; Herman, Don; Hazen, Terry C.; Firestone, Mary K.; Sutton, Steven R.

2005-01-01

Uranium mining and processing for nuclear weapons and fuel have left thousands of sites with toxic levels of this actinide in soil and ground water. An emerging strategy for remediating such environments involves using organic carbon to promote microbially-mediated reduction and precipitation of insoluble U(IV) minerals. Although previous U bioreduction studies have shown promising results, they were of short duration (up to a few months). Our longer-term (20 months) laboratory study using historically contaminated sediment has alarmingly shown that microbial reduction of U was transient even under reducing (methanogenic) conditions. Uranium was reductively immobilized during the first 100 days, but later (150 to 600 days) reoxidized and mobilized, although a microbial community capable of reducing U(VI) remained through the end of the experiment. The formation of Ca2UO2(CO3)3 complexes (caused by the elevated carbonate concentration from microbial respiration and presence of calcium) drove the U(IV)/U(VI) reduction potential to much more reducing conditions. Fe(III) and Mn(IV) were found to be likely terminal electron acceptors (TEAs) for U reoxidation. Thus, U remediation by organic carbon based reductive precipitation is not sustainable in calcareous, neutral to alkaline soils and ground waters

The spectrographic analysis of plutonium oxide or mixed plutonium oxide/uranium oxide fuel pellets by the dried residue technique

International Nuclear Information System (INIS)

Jarbo, G.J.; Faught, P.; Hildebrandt, B.

1980-05-01

An emission spectrographic method for the quantitative determination of metallic impurities in plutonium oxide and mixed plutonium oxide/uranium oxide is described. The fuel is dissolved in nitric acid and the plutonium and/or uranium extracted with tributyl phosphate. A small aliquot of the aqueous residue is dried on a 'mini' pyrolitic graphite plate and excited by high voltage AC spark in an oxygen atmosphere. Spectra are recorded in a region which has been specially selected to record simultaneously lines of boron and cadmium in the 2nd order and all the other elements of interest in the 1st order. Indium is used as an internal standard. The excitation of very small quantities of the uraniumm/plutonium free residue by high voltage spark, together with three separate levels of containment reduce the hazards to personnel and the environment to a minimum with limited effect on sensitivity and accuracy of the results. (auth)

Chemistry of uranium in evaporation pond sediment in the San Joaquin Valley, California, USA, using x-ray fluorescence and XANES techniques

International Nuclear Information System (INIS)

Duff, M.C.; Amrhein, C.; Bertsch, P.M.; Hunter, D.B.

1997-01-01

Evaporation ponds in the San Joaquin Valley (SJV), CA, used for the disposal of irrigation drainage waters, contain elevated levels of uranium. The ponds are filled periodically and support algae which upon evaporation become incorporated in the sediments as layers of decaying organic matter. This rich source of organic matter promotes reducing conditions in the sediments. Our research was conducted to characterize oxidation/reduction reactions that affect soluble and sediment U(IV)/U(VI) concentrations in the SJV ponds. Studies were done to (1) determine soluble U(Vl)/U(IV) in waters in contact with a pond sediment subjected to changes in redox status, (2) observe U solid oxidation state as a reducing pond sediment underwent (in vitro) oxidation, and (3) determine U solid oxidation state with respect to depth in pond surface sediment layers. Low pressure ion-exchange chromatography with an eluent of 0.125 M H 2 C 2 O 4 /0.25 M HNO 3 was used for the separation of U(IV) and U(VI) oxidation states in the drainage waters. Soluble U(VI) and U(IV) coexisted in sediment suspensions exposed to changes in redox potential (Eh) (-260 mV to +330 mV), and U(VI) was highly soluble in the oxidized, surface pond sediments. X-ray near edge absorption spectroscopy (XANES) showed that the U solid phases were 25% U(IV) and 75% U(VI) and probably a mixed solid [U 3 O 8(s) ] in highly reducing pond sediments. Sediment U(IV) increased slightly with depth in the surface pond sediment layers suggesting a gradual reduction of U(VI) to U(IV) with time. Under oxidized conditions, this mixed oxidation-state solid was highly soluble. 59 refs., 6 figs., 1 tab

Electrochemistry of uranium in sodium chloroaluminate melts

International Nuclear Information System (INIS)

D'olieslager, W.; Meuris, F.; Heerman, L.

1990-01-01

The electrochemical behaviour of uranium was studied in basic, NaCl-saturated NaAlCl 4 melts at 175 deg C. Solutions of UO 3 exhibit two oxidation/reduction waves (cyclic voltammetry). Analysis of the peak currents (cyclic voltammetry), the limiting currents (pulse polarography) and the non-linear log i-t curves (anodic controlled potential coulometry) leads to the conclusion that uranium(IV) in the basic chloroaluminate melt exists as two different species in slow equilibrium with one another, of which only one species can be oxidized to U(VI). (author) 16 refs.; 7 figs.; 3 tabs

Determination of kinetic coefficients for the simultaneous reduction of sulfate and uranium by Desulfovibrio desulfuricans bacteria

International Nuclear Information System (INIS)

Tucker, M.D.

1995-05-01

Uranium contamination of groundwaters and surface waters near abandoned mill tailings piles is a serious concern in many areas of the western United States. Uranium usually exists in either the U(IV) or the U(VI) oxidation state. U(VI) is soluble in water and, as a result, is very mobile in the environment. U(IV), however, is generally insoluble in water and, therefore, is not subject to aqueous transport. In recent years, researchers have discovered that certain anaerobic microorganisms, such as the sulfate-reducing bacteria Desulfovibrio desulfuricans, can mediate the reduction of U(VI) to U(IV). Although the ability of this microorganism to reduce U(VI) has been studied in some detail by previous researchers, the kinetics of the reactions have not been characterized. The purpose of this research was to perform kinetic studies on Desulfovibrio desulficans bacteria during simultaneous reduction of sulfate and uranium and to determine the phase in which uranium exists after it has been reduced and precipitated from solution. The studies were conducted in a laboratory-scale chemostat under substrate-limited growth conditions with pyruvate as the substrate. Kinetic coefficients for substrate utilization and cell growth were calculated using the Monod equation. The maximum rate of substrate utilization (k) was determined to be 4.70 days -1 while the half-velocity constant (K s ) was 140 mg/l COD. The yield coefficient (Y) was determined to be 0.17 mg cells/mg COD while the endogenous decay coefficient (k d ) was calculated as 0.072 days -1 . After reduction, U(IV) Precipitated from solution in the uraninite (UO 2 ) phase. Uranium removal efficiency as high as 90% was achieved in the chemostat

Nonaqueous chlorination of uranium metal in tributyl phosphate

International Nuclear Information System (INIS)

Buchikhin, E.P.; Kuznetsov, A.Yu.; Shatalov, V.V.; Vidanov, V.L.; Chekmarev, A.M.

2005-01-01

Low-temperature (30-50 deg C) chlorination of uranium metal in the TBP-TCE-Cl 2 system (TCE = tetrachloroethylene) was studied. Dissolution of uranium in the dipolar aprotic solvent proceeds with formation of U(IV) compounds. The activation energy of this process is 31.24 kJ mol -1 , and relative reaction order with respect to Cl 2 is 2. The effect of TBP concentration on chlorination was examined. The chlorination rate sharply increases at a water content in the TBP-TCE system of 0.2- 0.6 vol % [ru

Complexation of vanadium with amidoxime and carboxyl groups. Uncovering the competitive role of vanadium in uranium extraction from seawater

Energy Technology Data Exchange (ETDEWEB)

Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun [Chinese Academy of Sciences, Beijing (China). Inst. of High Energy Physics; Chai, Zhi-Fang [Chinese Academy of Sciences, Beijing (China). Inst. of High Energy Physics; Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences (RAD-X); Wu, Guo-Zhong [Chinese Academy of Sciences, Shanghai (China). Shanghai Inst. of Applied Physics

2017-09-01

At present, amidoxime-based adsorbents are considered to be the most promising materials for extraction of uranium from seawater. However, the high concentrations of transition metals especially vanadium strongly compete with uranium in the sequestration process, which is extremely limited the commercial use of amidoxime-based adsorbents. In this work, the coordination modes, bonding nature, and stabilities of possible vanadium(IV) (VO{sup 2+}) and (V) (VO{sub 2}{sup +}, VO{sup 3+}, V{sup 5+}) complexes with amidoximate (AO{sup -}), carboxyl (Ac{sup -}), glutarimidedioximate (HA{sup -}) and deprotonated glutarimidedioximate (A{sup 2-}) on single and double alkyl chains (R=C{sub 13}H{sub 26}) are systematically explored by quantum chemical calculations. Different from the uranyl (UO{sub 2}{sup 2+}) complexes, the AO{sup -} groups of the vanadium(IV) and (V) complexes prefer to coordinate as monodentate and chelate ligands, while few species with AO{sup -} groups in η{sup 2}-binding mode have been observed in the vanadium complexes. Besides, the vanadium complexes are predicted to have obvious covalent metal-ligand bonds. According to thermodynamic stability analysis, all the vanadium complexes with AO{sup -}, Ac{sup -}, HA{sup -} and A{sup 2-} ligands on double alkyl chains are found to be more stable than corresponding complexes with ligands on a single chain. The synergistic effect of the amidoxime and carboxyl groups can be observed in most of VO{sub 2}{sup +} and VO{sup 3+} complexes with mixed ligands (AO{sup -}/Ac{sup -}). The vanadium(IV) and (V) complexes are more stable than the corresponding uranyl complexes, and the adsorption capability of the amidoxime-based adsorbents toward vanadium(V) ions decrease in the order of VO{sub 2}{sup +}>VO{sup 3+}> V{sup 5+}. The dioxovanadium cation VO{sub 2}{sup +} is predicted to form multinuclear vanadium complex in the sequestration process, possibly resulting in higher stable VO{sub 2}{sup +} complexes. Therefore

Uranium Sequestration During Biostimulated Reduction and In Response to the Return of Oxic Conditions In Shallow Aquifers

Science.gov (United States)

Fuller, Christopher C.; Johnson, Kelly J.; Akstin, Katherine; Singer, David M.; Yabusaki, Steven B.; Fang, Yilin; Fuhrmann, M.

2015-01-01

A proposed approach for groundwater remediation of uranium contamination is to generate reducing conditions by stimulating the growth of microbial populations through injection of electron donor compounds into the subsurface. Sufficiently reducing conditions will result in reduction of soluble hexavalent uranium, U(VI), and precipitation of the less soluble +4 oxidation state uranium, U(IV). This process is termed biostimulated reduction. A key issue in the remediation of uranium (U) contamination in aquifers by biostimulated reduction is the long term stability of the sequestered uranium. Three flow-through column experiments using aquifer sediment were used to evaluate the remobilization of bioreduced U sequestered under conditions in which biostimulation extended well into sulfate reduction to enhance precipitation of reduced sulfur phases such as iron sulfides. One column received added ferrous iron, Fe(II), increasing production of iron sulfides, to test their effect on remobilization of the sequestered uranium, either by serving as a redox buffer by competing for dissolved oxygen, or by armoring the reduced uranium. During biostimulation of the ambient microbial population with acetate, dissolved uranium was lowered by a factor of 2.5 or more with continued removal for over 110 days of biostimulation, well after the onset of sulfate reduction at ~30 days. Sequestered uranium was essentially all U(IV) resulting from the formation of nano-particulate uraninite that coated sediment grains to a thickness of a few 10’s of microns, sometimes in association with S and Fe. A multicomponent biogeochemical reactive transport model simulation of column effluents during biostimulation was generally able to describe the acetate oxidation, iron, sulfate, and uranium reduction for all three columns using parameters derived from simulations of field scale biostimulation experiments. Columns were eluted with artificial groundwater at equilibrium with atmospheric oxygen to

URANIUM-SERIES CONSTRAINTS ON RADIONUCLIDE TRANSPORT AND GROUNDWATER FLOW AT NOPAL I URANIUM DEPOSIT, SIERRA PENA BLANCA, MEXICO

Energy Technology Data Exchange (ETDEWEB)

S. J. Goldstein, S. Luo, T. L. Ku, and M. T. Murrell

2006-04-01

Uranium-series data for groundwater samples from the vicinity of the Nopal I uranium ore deposit are used to place constraints on radionuclide transport and hydrologic processes at this site, and also, by analogy, at Yucca Mountain. Decreasing uranium concentrations for wells drilled in 2003 suggest that groundwater flow rates are low (< 10 m/yr). Field tests, well productivity, and uranium isotopic constraints also suggest that groundwater flow and mixing is limited at this site. The uranium isotopic systematics for water collected in the mine adit are consistent with longer rock-water interaction times and higher uranium dissolution rates at the front of the adit where the deposit is located. Short-lived nuclide data for groundwater wells are used to calculate retardation factors that are on the order of 1,000 for radium and 10,000 to 10,000,000 for lead and polonium. Radium has enhanced mobility in adit water and fractures near the deposit.

URANIUM-SERIES CONSTRAINTS ON RADIONUCLIDE TRANSPORT AND GROUNDWATER FLOW AT NOPAL I URANIUM DEPOSIT, SIERRA PENA BLANCA, MEXICO

International Nuclear Information System (INIS)

S. J. Goldstein, S. Luo, T. L. Ku, and M. T. Murrell

2006-01-01

Uranium-series data for groundwater samples from the vicinity of the Nopal I uranium ore deposit are used to place constraints on radionuclide transport and hydrologic processes at this site, and also, by analogy, at Yucca Mountain. Decreasing uranium concentrations for wells drilled in 2003 suggest that groundwater flow rates are low (< 10 m/yr). Field tests, well productivity, and uranium isotopic constraints also suggest that groundwater flow and mixing is limited at this site. The uranium isotopic systematics for water collected in the mine adit are consistent with longer rock-water interaction times and higher uranium dissolution rates at the front of the adit where the deposit is located. Short-lived nuclide data for groundwater wells are used to calculate retardation factors that are on the order of 1,000 for radium and 10,000 to 10,000,000 for lead and polonium. Radium has enhanced mobility in adit water and fractures near the deposit

U{sub x}Th{sub 1-x}(C{sub 2}O{sub 4}){sub 2} solide characterisation studies

Energy Technology Data Exchange (ETDEWEB)

Carrigan, C.; Taylor, R.; Sarsfield, M. [National Nuclear Laboratory, Sellafield, Seascale, Cumbria, CA20 1PG (United Kingdom)

2016-07-01

Many advanced reprocessing schemes under development are aimed at co-processing and co-conversion of actinides, unlike current reprocessing plants that produce separate uranium and plutonium products. The most well developed option for the co-conversion stage is probably oxalate co-precipitation, followed by the thermal co-conversion to a mixed oxide product. It is thus envisaged that future processes will avoid separation of plutonium from uranium and instead allow part of the uranium to flow with the plutonium, resulting in co-precipitation as the oxalate, and finally co-conversion to a mixed uranium-plutonium oxide (MOX), which can be fabricated into recycled nuclear fuel for further energy generation. The co-crystallisation of uranium (IV) and plutonium (III) into a single oxalate structure ensures the homogenous distribution of the 2 actinides at the molecular scale. The joint conversion of uranium and plutonium to the oxide form makes it possible to remove the complicated step of blending and grinding the 2 distinct oxide powders, as currently employed for the purposes of MOX fuel fabrication. This concept can also be extended to other actinides, including minor actinides from partitioning processes such as SANEX (Selective Actinide Extraction) and GANEX (Grouped Actinide Extraction) processes or even a thorium containing product from recycle of thorium based fuels. A selection of U{sub x}Th{sub 1-x}(C{sub 2}O{sub 4}){sub 2} solids at varying concentrations of uranium and thorium were prepared by oxalate co-precipitation. Uranium (VI) was conditioned electrochemically at -0.7 V to uranium (IV), in the presence of hydrazine. The reduced uranium (IV) in nitric acid was mixed with thorium nitrate solutions at different concentration ratios with oxalic acid. The mixed tetravalent uranium-thorium oxalate solid products have been characterised by Raman and IR spectroscopies. The influence of thorium substituted into the uranium oxalate structure was evaluated

U_xTh_1_-_x(C_2O_4)_2 solide characterisation studies

International Nuclear Information System (INIS)

Carrigan, C.; Taylor, R.; Sarsfield, M.

2016-01-01

Many advanced reprocessing schemes under development are aimed at co-processing and co-conversion of actinides, unlike current reprocessing plants that produce separate uranium and plutonium products. The most well developed option for the co-conversion stage is probably oxalate co-precipitation, followed by the thermal co-conversion to a mixed oxide product. It is thus envisaged that future processes will avoid separation of plutonium from uranium and instead allow part of the uranium to flow with the plutonium, resulting in co-precipitation as the oxalate, and finally co-conversion to a mixed uranium-plutonium oxide (MOX), which can be fabricated into recycled nuclear fuel for further energy generation. The co-crystallisation of uranium (IV) and plutonium (III) into a single oxalate structure ensures the homogenous distribution of the 2 actinides at the molecular scale. The joint conversion of uranium and plutonium to the oxide form makes it possible to remove the complicated step of blending and grinding the 2 distinct oxide powders, as currently employed for the purposes of MOX fuel fabrication. This concept can also be extended to other actinides, including minor actinides from partitioning processes such as SANEX (Selective Actinide Extraction) and GANEX (Grouped Actinide Extraction) processes or even a thorium containing product from recycle of thorium based fuels. A selection of U_xTh_1_-_x(C_2O_4)_2 solids at varying concentrations of uranium and thorium were prepared by oxalate co-precipitation. Uranium (VI) was conditioned electrochemically at -0.7 V to uranium (IV), in the presence of hydrazine. The reduced uranium (IV) in nitric acid was mixed with thorium nitrate solutions at different concentration ratios with oxalic acid. The mixed tetravalent uranium-thorium oxalate solid products have been characterised by Raman and IR spectroscopies. The influence of thorium substituted into the uranium oxalate structure was evaluated. Several vibrational modes

In situ Microbial Community Control of the Stability of Bio-Reduced Uranium

International Nuclear Information System (INIS)

Long, Phillip E.; McKinley, James P.; White, David C.

2006-01-01

In aerobic aquifers typical of many Department of Energy (DOE) legacy waste sites, uranium is present in the oxidized U(VI) form which is soluble and thus mobile compared to U(IV). Previous work at the Old Rifle Uranium Mill Tailings Remedial Action (UMTRA) site demonstrated that biostimulation by acetate injection promoted growth of Geobacteraceae and stimulated the microbial reduction of U(VI) to less soluble U(IV) (1, 4). Despite the potential for oxidative dissolution of bio-reduced U(IV), field experiments at the Old Rifle site show that although the rate of U(VI) reduction decreases following the on-set of sulfate reduction, U(VI) reduction continues even following the cessation of acetate injection (1, 4). However, U(VI) reduction is reversible and the basis for the observed maintenance of U(VI) reduction post-stimulation is a critical but as yet unresolved issue for the application of biostimulation as a treatment technology. The continued U(VI) reduction and the maintenance of reduced U(IV) may result from many factors including U(VI) reduction by sulfate reducing bacteria (SRB), generation of H2S or FeS0.9 which serves as an oxygen sink, or the preferential sorption of U(VI) by microbial cells or biopolymers. The overall goal of the project is to develop an understanding of the mechanisms for the maintenance of bio-reduced uranium in an aerobic aquifer under field conditions following the cessation of electron donor addition

Simultaneous removal and recovery of uranium from aqueous solution using TiO_2 photoelectrochemical reduction method

International Nuclear Information System (INIS)

Huichao He; Meirong Zong; Faqin Dong; Southwest University of Science and Technology, Sichuan; Pengpan Yang; Gaili Ke; Mingxue Liu; Xiaoqin Nie; Wei Ren; Liang Bian; Southwest University of Science and Technology, Sichuan; Chinese Academy of Sciences, Xinjiang

2017-01-01

U(VI)-containing wastewater has potential radiation hazard to the environment, but contains valuable uranium resource. Based on the reduction of U(VI) and the difference in solubility between U(VI) and U(IV), here we construct a TiO_2-based photoelectrochemical cell to remove U(VI) and recover uranium from aqueous solution. By irradiating TiO_2 photoanode at E = 0.45 V versus SCE, U(VI) can be simultaneously removed from aqueous solution and recovered as solid uranium compounds on a FTO glass cathode. Since ethanol can act as hole scavenger to protect the formed U(IV) and provide CO_2"−"· as reductant, ethanol adding improved the U(VI) reduction efficiency of TiO_2-based photoelectrochemical cell. (author)

Coordination compounds of titanium, zirconium, tin, thorium and uranium

International Nuclear Information System (INIS)

Deshpande, S.G.; Jain, S.C.

1990-01-01

Reactions of isatin, furoic acid and picolinic acid have been carried out with titanium tetrachloride, tin tetrachloride, thorium tetrachloride, zirconyl chloride and uranyl nitrate. While 2:3(metal:ligand) type compounds of isatin have been obtained with Ti(IV) and Sn(IV), zirconium(IV), thorium(IV), and uranium(VI) do not react with the ligand under similar experimental conditions. Furoic acid (FAH) and picolinic acid(PicH) form various chloro furoates and picolinates when reacted with TiCl 4 , ZrOCl 2 and ThCl 4 , but do not react with SnCl 4 . The various compounds synthesised have been characterised on the basis of elemental analysis, infrared studies, conductivity and thermogravimetric measurements. (author). 1 tab., 10 refs

Uranium Mobility During In Situ Redox Manipulation of the 100 Areas of the Hanford Site

International Nuclear Information System (INIS)

Resch, C.T.; Szecsody, J.E.; Fruchter, J.S.; Cantrell, K.J.; Krupka, K.M.; Williams, M.D.

1998-01-01

A series of laboratory experiments and computer simulations was conducted to assess the extent of uranium remobilization that is likely to occur at the end of the life cycle of an in situ sediment reduction process. The process is being tested for subsurface remediation of chromate- and chlorinated solvent-contaminated sediments at the Hanford Site in southeastern Washington. Uranium species that occur naturally in the +6 valence state ∼(VI) at 10 ppb in groundwater at Hanford will accumulate as U(N) through the reduction and subsequent precipitation conditions of the permeable barrier created by in situ redox manipulation. The precipitated uranium will W remobilized when the reductive capacity of the barrier is exhausted and the sediment is oxidized by the groundwater containing dissolved oxygen and other oxidants such as chromate. Although U(N) accumulates from years or decades of reduction/precipitation within the reduced zone, U(W) concentrations in solution are only somewhat elevated during aquifer oxidation because oxidation and dissolution reactions that release U(N) precipitate to solution are slow. The release rate of uranium into solution was found to be controlled mainly by the oxidation/dissolution rate of the U(IV) precipitate (half-life 200 hours) and partially by the fast oxidation of adsorbed Fe(II) (half- life 5 hours) and the slow oxidation of Fe(II)CO 3 (half-life 120 hours) in the reduced sediment. Simulations of uranium transport that incorporated these and other reactions under site-relevant conditions indicated that 35 ppb U(VI) is the maximum concentration likely to result from mobilization of the precipitated U(IV) species. Experiments also indicated that increasing the contact time between the U(IV) precipitates and the reduced sediment, which is likely to occur in the field, results in a slower U(IV) oxidation rate, which, in turn, would lower the maximum concentration of mobilized U(W). A six-month-long column experiment confirmed that

Depleted uranium hexafluoride: Waste or resource?

Energy Technology Data Exchange (ETDEWEB)

Schwertz, N.; Zoller, J.; Rosen, R.; Patton, S. [Lawrence Livermore National Lab., CA (United States); Bradley, C. [USDOE Office of Nuclear Energy, Science, Technology, Washington, DC (United States); Murray, A. [SAIC (United States)

1995-07-01

the US Department of Energy is evaluating technologies for the storage, disposal, or re-use of depleted uranium hexafluoride (UF{sub 6}). This paper discusses the following options, and provides a technology assessment for each one: (1) conversion to UO{sub 2} for use as mixed oxide duel, (2) conversion to UO{sub 2} to make DUCRETE for a multi-purpose storage container, (3) conversion to depleted uranium metal for use as shielding, (4) conversion to uranium carbide for use as high-temperature gas-cooled reactor (HTGR) fuel. In addition, conversion to U{sub 3}O{sub 8} as an option for long-term storage is discussed.

Tris(bis(trimethylsilyl)amido)uranium: Compounds with tri-, tetra-, and penta-valent uranium

Energy Technology Data Exchange (ETDEWEB)

Stewart, J.L.

1988-04-01

This trivalent uranium compound, serves as a precursor to new tri-, tetra-, and penta-valent uranium species. The geometry about the U atom is pyramidal. Lewis-base coordination compounds of U(N(SiMe/sub 3/)/sub 2/)/sub 3/ with a one-to-one- ratio of Lewis base to uranium were isolated with pyridine, 4-dimethylamino-pyridine, 2,6-Me/sub 2/-C/sub 6/H/sub 3/NC, and TPO. Two-to-one coordination compounds were obtained with t-butylnitrile and t-butylisocyanide. Compounds with more sterically demanding bases could not be isolated. The expected decrease in U-N(SiMe/sub 3/)/sub 2/ bond length with increase in oxidation state is not observed. Reaction of ClU(N(SiMe/sub 3/)/sub 2/)/sub 3/and Li(NH(p-tolyl)) yields the uranium (IV) dimer, U/sub 2/(N(SiMe/sub 3/)/sub 2/)/sub 4/(..mu..-N(p-tolyl))/sub 2/. Reaction with 2,4,6-triemethylaniline produces a dimer. Analogous substitution products could not be obtained with aniline or p-toluidine. t-Bu/sub 3/CO/sup /minus//, t-Bu/sub 2/CHO/sup /minus//, and t-Bu/sub 3/SiO/sup /minus// are used to synthesize new tetravalent, mononuclear uranium compounds. Reaction of ClU(tritox)/sub 3/ with alkyllithium reagents leads to isolation of RU(tritox)/sub 3/. The reaction of U(ditox)/sub 4/ with MeLi affords the addition product U(ditox)/sub 4/(Me)Li, whose crystal structure is described. Preparation of uranium silox compounds is reported. 97 refs., 26 figs., 39 tabs.

Mathematical modeling of the radiation-chemical oxidation of U(IV) in HClO4

International Nuclear Information System (INIS)

Vladimirova, M.V.

1995-01-01

Mathematical modeling of U(IV) oxidation in 0.5-12 M HClO 4 upon α, γ-radiolysis, based on the proposed scheme of radiation-chemical reactions, has been performed. The rate constants of the U(VI) + HO 2 , U(IV) + HO 2 , U(IV) + ClO 2 , and U(IV) + ClO 2 - reactions have been determined by the comparison of the calculated and experimental kinetic and dose curves and radiation-chemical yields of U(IV) oxidation or U(VI) formation. General equations for uranium (IV) oxidation constants at various HClO 4 concentrations, based on the analysis of the rates of particular radiation-chemical reactions composing oxidation process, have been obtained

The combined measurement of uranium by alpha spectrometry and secondary ion mass spectrometry (SIMS)

International Nuclear Information System (INIS)

Harvan, D.

2009-01-01

The aim of thesis was to found the dependence between radiometric method - alpha spectrometry and surface sensitive method - Secondary Ion Mass Spectrometry (SIMS). Uranium or naturally occurring uranium isotopes were studied. Samples (high polished stainless steel discs) with uranium isotopes were prepared by electrodeposition. Samples were measured by alpha spectrometry after electrodeposition and treatment. It gives surface activities. Weights, as well as surface's weights of uranium isotopes were calculated from their activities, After alpha spectrometry samples were analyzed by TOF-SIMS IV instrument in International Laser Centre in Bratislava. By the SIMS analysis intensities of uranium-238 were obtained. The interpretation of SIMS intensities vs. surface activity, or surface's weights of uranium isotopes indicates the possibility to use SIMS in quantitative analysis of surface contamination by uranium isotopes, especially 238 U. (author)

Laser-induced breakdown spectroscopy measurements of uranium and thorium powders and uranium ore

Energy Technology Data Exchange (ETDEWEB)

Judge, Elizabeth J. [Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Barefield, James E., E-mail: jbarefield@lanl.gov [Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Berg, John M. [Manufacturing Engineering and Technology Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Clegg, Samuel M.; Havrilla, George J.; Montoya, Velma M.; Le, Loan A.; Lopez, Leon N. [Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

2013-05-01

Laser-induced breakdown spectroscopy (LIBS) was used to analyze depleted uranium and thorium oxide powders and uranium ore as a potential rapid in situ analysis technique in nuclear production facilities, environmental sampling, and in-field forensic applications. Material such as pressed pellets and metals, has been extensively studied using LIBS due to the high density of the material and more stable laser-induced plasma formation. Powders, on the other hand, are difficult to analyze using LIBS since ejection and removal of the powder occur in the laser interaction region. The capability of analyzing powders is important in allowing for rapid analysis of suspicious materials, environmental samples, or trace contamination on surfaces since it most closely represents field samples (soil, small particles, debris etc.). The rapid, in situ analysis of samples, including nuclear materials, also reduces costs in sample collection, transportation, sample preparation, and analysis time. Here we demonstrate the detection of actinides in oxide powders and within a uranium ore sample as both pressed pellets and powders on carbon adhesive discs for spectral comparison. The acquired LIBS spectra for both forms of the samples differ in overall intensity but yield a similar distribution of atomic emission spectral lines. - Highlights: • LIBS analysis of mixed actinide samples: depleted uranium oxide and thorium oxide • LIBS analysis of actinide samples in powder form on carbon adhesive discs • Detection of uranium in a complex matrix (uranium ore) as a precursor to analyzing uranium in environmental samples.

Fluorine and chlorine determination in mixed uranium-plutonium oxide fuel and plutonium dioxide

International Nuclear Information System (INIS)

Elinson, S.V.; Zemlyanukhina, N.A.; Pavlova, I.V.; Filatkina, V.P.; Tsvetkova, V.T.

1981-01-01

A technique of fluorine and chlorine determination in the mixed uranium-plutonium oxide fuel and plutonium dioxide, based on their simultaneous separation by means of pyrohydrolysis, is developed. Subsequently, fluorine is determined by photometry with alizarincomplexonate of lanthanum or according to the weakening of zirconium colouring with zylenol orange. Chlorine is determined using the photonephelometric method according to the reaction of chloride-ion interaction with silver nitrate or by spectrophotometric method according to the reaction with mercury rhodanide. The lower limit of fluorine determination is -6x10 -5 %, of chlorine- 1x10 -4 % in the sample of 1g. The relative mean quadratic deviation of the determination result (Ssub(r)), depends on the character of the material analyzed and at the content of nx10 -4 - nx10 -3 mass % is equal to from 0.05 to 0.32 for fluorine and from 0.11 to 0.35 for chlorine [ru

Enhanced Uranium Immobilization and Reduction by Geobacter sulfurreducens Biofilms

Science.gov (United States)

Cologgi, Dena L.; Speers, Allison M.; Bullard, Blair A.; Kelly, Shelly D.

2014-01-01

Biofilms formed by dissimilatory metal reducers are of interest to develop permeable biobarriers for the immobilization of soluble contaminants such as uranium. Here we show that biofilms of the model uranium-reducing bacterium Geobacter sulfurreducens immobilized substantially more U(VI) than planktonic cells and did so for longer periods of time, reductively precipitating it to a mononuclear U(IV) phase involving carbon ligands. The biofilms also tolerated high and otherwise toxic concentrations (up to 5 mM) of uranium, consistent with a respiratory strategy that also protected the cells from uranium toxicity. The enhanced ability of the biofilms to immobilize uranium correlated only partially with the biofilm biomass and thickness and depended greatly on the area of the biofilm exposed to the soluble contaminant. In contrast, uranium reduction depended on the expression of Geobacter conductive pili and, to a lesser extent, on the presence of the c cytochrome OmcZ in the biofilm matrix. The results support a model in which the electroactive biofilm matrix immobilizes and reduces the uranium in the top stratum. This mechanism prevents the permeation and mineralization of uranium in the cell envelope, thereby preserving essential cellular functions and enhancing the catalytic capacity of Geobacter cells to reduce uranium. Hence, the biofilms provide cells with a physically and chemically protected environment for the sustained immobilization and reduction of uranium that is of interest for the development of improved strategies for the in situ bioremediation of environments impacted by uranium contamination. PMID:25128347

Synthesis and structural characterisation of mixed An(IV)-An(III) actinide oxalates used as precursors for dedicated fuel or target

International Nuclear Information System (INIS)

Tamain, Christelle; Grandjean, Stephane; Arab Chapelet, Benedicte; Abraham, Francis

2010-01-01

Oxalic co-conversion process plays an important role by producing mixed-actinide compounds used as starting materials as they are particularly suitable precursors of actinide oxide solid solutions. In these oxalate compounds, a mixed crystallographic site which accommodates both elements in spite of their different oxidation states has been established. The charge compensation is ensured by monovalent cations present in the acidic solution. This communication reviews the various mixed-actinide oxalates obtained by crystallization from acidic solution. First, crystallographic structures determined by X-ray diffraction from single crystals are described. Then completing data obtained by powder X-ray diffraction are presented on various systems. The different supramolecular arrangements underline the complexity of An(IV)-An(III)/Ln(III) oxalate system and the need to pursue studies on single crystals. (authors)

Synthesis of new triphosphonic esters for uranium extraction in phosphoric medium

International Nuclear Information System (INIS)

Sturtz, Georges; Pensec, Thierry

1981-01-01

Triphosphonic acids obtained by nucleophilic addition of dialkyl phosphites on ethylenic diphosphonates are partially hydrolysed into incompletely esterified triphosphonic acids. Their extracting properties for uranium-IV in phosphonic medium are tested [fr

Crystal and molecular structure of tetrathiocyanato tetrakis (triphenylphosphine oxide)uranium(IV)

Energy Technology Data Exchange (ETDEWEB)

Bombieri, G; De Paoli, G; Forsellini, E [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi; Brown, D

1979-01-01

The crystal structure of the title compound has been determined from three dimensional X-ray diffraction data. The space group and lattice parameters are given. The asymmetric unit comprises two independent U(NCS)/sub 4/(tppo)/sub 4/ molecules in each of which the coordination polyhedron around the uranium atom is close to square antiprismatic.

Comparison of physical chemical properties of powders and respirable aerosols of industrial mixed uranium and plutonium oxide fuels

International Nuclear Information System (INIS)

Eidson, A.F.

1982-01-01

Studies were performed to characterize physical and chemical properties which may be important in determining the metabolism of accidentally released, inhaled aerosols of industrial mixed uranium and plutonium oxide fuels and to compare the properties of bulk powders and the respirable fraction they include. X-ray diffraction measurements showed that analysis of mixed-oxide powders from four process steps served to characterize their respirable fractions. IR spectroscopy was useful as a method to detect organic binders that were not observed by X-ray diffraction methods. Both X-ray diffraction and IR spectroscopy methods can be used in combination to identify the sources of a complex aerosol that might be released from more than one fabrication step. Isotopic distributions in powders and aerosols showed that information important for radiation dose to tissue calculations or Pu lung burden estimates can be obtained by analysis of powders. (U.K.)

Bioremediation of ground water contaminants at a uranium mill tailings site

International Nuclear Information System (INIS)

Barton, L.L.; Nuttall, H.E.; Thomson, B.M.; Lutze, W.

1995-01-01

Ground water contaminated with uranium from milling operations must be remediated to reduce the migration of soluble toxic compounds. At the mill tailings site near Tuba City, Arizona (USA) the approach is to employ bioremediation for in situ immobilization of uranium by bacterial reduction of uranyl, U(VI), compounds to uraninite, U(IV). In this initial phase of remediation, details are provided to indicate the magnitude of the contamination problem and to present preliminary evidence supporting the proposition that bacterial immobilization of uranium is possible. Additionally, consideration is given to contaminating cations and anions that may be at toxic levels in ground water at this uranium mill tailing site and detoxification strategies using bacteria are addressed. A model concept is employed so that results obtained at the Tuba City site could contribute to bioremediation of ground water at other uranium mill tailings sites

χ{sup (3)} measurements of axial ligand modified high valent tin(IV) porphyrins using degenarete four wave mixing at 532nm

Energy Technology Data Exchange (ETDEWEB)

Narendran, N. K. Siji, E-mail: sijinarendran@gmail.com; Chandrasekharan, K. [Laser and nonlinear optics laboratory, Department of Physics, National Institute of Technology Calicut, Calicut-673601, Kerala (India); Soman, Rahul; Arunkumar, Chellaiah [Bioinorganic materials laboratory, Department of Chemistry, National Institute of Technology Calicut, Calicut-673601, Kerala (India); Sudheesh, P. [Department of Physics, VTM NSS College, Dhanuvachapuram, Thiruvananthapuram (India)

2014-10-15

Porphyrins and metalloporphyrins are unique class of molecules for Nonlinear Optical applications because of their unique structure of altering the central metal atom, large extended π-system, high thermal stability, tunable shape, symmetry and synthetic versatility Here, we report χ{sup (3)} Measurements of a simple phenyl porphyrins and its highvalent tin(IV) porphyrins with Bromination characterized by UV-Visible spectroscopic method. In this study, we employed the Degenerate Four Wave Mixing technique using forward Boxcar geometry with an Nd:YAG nano second pulsed laser as source and it was found that the tin(IV) porphyrin with Bromination exhibits good χ{sup (3)} value and figure of merit.

Subcellular distribution of uranium in the roots of Spirodela punctata and surface interactions

Energy Technology Data Exchange (ETDEWEB)

Nie, Xiaoqin, E-mail: xiaoqin_nie@163.com [Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory, Mianyang 621010 (China); Key Laboratory of Radiation Physics and Technology (Sichuan University), Ministry of Education, Institute of Nuclear Science and Technology, Sichuan University, Chengdu 610064 (China); Dong, Faqin, E-mail: fqdong2004@163.com [Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory, Mianyang 621010 (China); Liu, Ning [Key Laboratory of Radiation Physics and Technology (Sichuan University), Ministry of Education, Institute of Nuclear Science and Technology, Sichuan University, Chengdu 610064 (China); Liu, Mingxue [Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory, Mianyang 621010 (China); Zhang, Dong; Kang, Wu [Institute of Nuclear Physics and Chemistry,China Academy of Engineering Physics, Mianyang 621900 (China); Sun, Shiyong; Zhang, Wei; Yang, Jie [Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory, Mianyang 621010 (China)

2015-08-30

Graphical abstract: - Highlights: • The proportion of uranium concentration approximate as 8:2:1 in the cell wall organelle and cytosol fractions of roots of S. punctata. • The particles including 35% Fe (wt%) released from the cells after 100 mg/L U treatment 48 h. • Most of the uranium bound onto the root surface and contacted with phosphorus ligands and formed as nano-scales U-P lamellar crystal. • FTIR and XPS analyses result indicates the uranium changed the band position and shapes of phosphate group, and the region of characteristic peak belongs to U(VI) and U(IV) were also observed. - Abstract: The subcellular distribution of uranium in roots of Spirodela punctata (duckweed) and the process of surface interaction were studied upon exposure to U (0, 5–200 mg/L) at pH 5. The concentration of uranium in each subcelluar fraction increased significantly with increasing solution U level, after 200 mg/L uranium solution treatment 120 h, the proportion of uranium concentration approximate as 8:2:1 in the cell wall organelle and cytosol fractions of roots of S. punctata. OM SEM and EDS showed after 5–200 mg/L U treatment 4–24 h, some intracellular fluid released from the root cells, after 100 mg/L U treatment 48 h, the particles including 35% Fe (wt%) and other organic matters such as EPS released from the cells, most of the uranium bound onto the root surface and contacted with phosphorus ligands and formed as nano-scales U-P lamellar crystal, similar crystal has been found in the cell wall and organelle fractions after 50 mg/L U treatment 120 h. FTIR and XPS analyses result indicates the uranium changed the band position and shapes of phosphate group, and the region of characteristic peak belongs to U(VI) and U(IV) were also observed.

Accountability methods for plutonium and uranium: the NRC manuals

Energy Technology Data Exchange (ETDEWEB)

Gutmacher, R.G.; Stephens, F.B.

1977-09-28

Four manuals containing methods for the accountability of plutonium nitrate solutions, plutonium dioxide, uranium dioxide and mixed uranium-plutonium oxide have been prepared by us and issued by the U.S. Nuclear Regulatory Commission. A similar manual on methods for the accountability of uranium and plutonium in reprocessing plant dissolver solutions is now in preparation. In the present paper, we discuss the contents of the previously issued manuals and give a preview of the manual now being prepared.

Accountability methods for plutonium and uranium: the NRC manuals

International Nuclear Information System (INIS)

Gutmacher, R.G.; Stephens, F.B.

1977-01-01

Four manuals containing methods for the accountability of plutonium nitrate solutions, plutonium dioxide, uranium dioxide and mixed uranium-plutonium oxide have been prepared by us and issued by the U.S. Nuclear Regulatory Commission. A similar manual on methods for the accountability of uranium and plutonium in reprocessing plant dissolver solutions is now in preparation. In the present paper, we discuss the contents of the previously issued manuals and give a preview of the manual now being prepared

The collection of uranium from sea water with hydrous metal oxide, 2

International Nuclear Information System (INIS)

Yamashita, Hisao; Nakajima, Fumito; Ozawa, Yoshihiro; Murata, Toshifumi.

1980-01-01

The mechanism of uranium adsorption from sea water by hydrous titanium(IV) oxide was investigated. The uranium adsorption experiments were conducted using a solution containing NaCl, NaHCO 3 , and uranium. Thermochemical calculation showed that the tris(carbonato)dioxouranate(VI) ion (UO 2 (CO 3 ) 3 ) 4- found in sea water existed in the solution at pH 8 and 25 0 C. The uranium uptake varied with the pH of the solution, exhibiting a minimum value at pH 8. The enthalpy change, delta H, and the activation energy, E, of the uranium adsorption were found to be 23.6 kJ mol -1 and 52.7 kJ mol -1 respectively. The analysis of carbonate in the adsorbent showed that the carbonate ion in(UO 2 (CO 3 ) 3 ) 4- was released into the solution during the uranium adsorption. On the basis of the present experimental results, the mechanism of uranium adsorption was discussed. (author)

Adsorption study for uranium in Rocky Flats groundwater

International Nuclear Information System (INIS)

Laul, J.C.; Rupert, M.C.; Harris, M.J.; Duran, A.

1995-01-01

Six adsorbents were studied to determine their effectiveness in removing uranium in Rocky Flats groundwater. The bench column and batch (Kd) tests showed that uranium can be removed (>99.9%) by four adsorbents. Bone Charcoal (R1O22); F-1 Alumina (granular activated alumina); BIOFIX (immobilized biological agent); SOPBPLUS (mixed metal oxide); Filtrasorb 300 (granular activated carbon); and Zeolite (clinoptilolite)

Uranium isotope separation using styrene cation exchangers

International Nuclear Information System (INIS)

Kahovec, J.

1980-01-01

The separation of 235 U and 238 U isotopes is carried out either by simple isotope exchange in the system uranium-cation exchanger (sulphonated styrene divinylbenzene resin), or by combination of isotope exchange in a uranium-cation exchanger (Dowex 50, Amberlite IR-120) system and a chemical reaction. A review is presented of elution agents used, the degree of cation exchanger cross-linking, columns length, and 235 U enrichment. The results are described of the isotope effect study in a U(IV)-U(VI)-cation exchanger system conducted by Japanese and Romanian authors (isotope exchange kinetics, frontal analysis, reverse (indirect) frontal analysis). (H.S.)

Irradiated uranium reprocessing, Final report I-VI, IV Deo IV - Separation of uranium, plutonium and fission products from the irradiated fuel of the reactor in Vinca; Prerada ozracenog urana. Zavrsni izvestaj - I-VI, IV Deo - Odvajanje urana, plutonijuma i fisionih produkata iz isluzenog goriva reaktora u Vinci

Energy Technology Data Exchange (ETDEWEB)

Gal, I [Institute of Nuclear Sciences Boris Kidric, Laboratorija za visoku aktivnost, Vinca, Beograd (Serbia and Montenegro)

1961-12-15

This study describes the technology for separation of uranium, plutonium and fission products from the radioactive water solution which is obtained by dissolving the spent uranium fuel from the reactor in Vinca. The procedure should be completed in a hot cell, with the maximum permitted activity of 10 Ci.

The uranium International trade

International Nuclear Information System (INIS)

Gonzalez U, L.A.

1993-01-01

The aim of this thesis is the understanding of how the present dynamic of uranium International trade is developed, the variables which fall into, the factors that are affecting and conditioning it, in order to clarify which are going to be the outlook in the future of this important resource in front of the present ecological situation and the energetic panorama of XXI Century. For this purpose, as starting point, the uranium is considered as a strategic material which importance take root in its energetic potential as alternate energy source, and for this reason in Chapter I, the general problem of raw materials, its classification and present situation in the global market is presented. In Chapter II, by means of a historical review, is explain what uranium is, how it was discovered, and how since the end of the past Century and during the last three decades of present, uranium pass of practically unknown element, to the position of a strategic raw material, which by degrees, generate an International market, owing to its utilization as a basic resource in the generation of energy. Chapter III, introduce us in the roll played by uranium, since its warlike applications until its utilization in nuclear reactors for the generation of electricity. Also is explain the reason for this change in the perception at global level. Finally, in Chapter IV we enter upon specifically in the present conditions of the International market of this mineral throughout the trends of supply and demand, the main producers, users, price dynamics, and the correlation among these economical variables and other factors of political, social and ecological nature. All of these with the purpose to found out, if there exist, a meaning of the puzzle that seems to be the uranium International trade

X-ray spectroscopic studies of microbial transformations of uranium

International Nuclear Information System (INIS)

Dodge, C.J.; Francis, A.J.; Clayton, C.R.

1995-10-01

Several uranium compounds U-metal (α-phase), UO 2 , U 3 O 8 , γ-UO 3 , uranyl acetate, uranyl nitrate, uranyl sulfate, aqueous and solid forms of 1:1 U:citric acid and 1:1:2 U:Fe:citric acid mixed-metal complexes, and a precipitate obtained by photodegradation of the U-citrate complex were characterized by X-ray spectroscopy using XPS, XANES, and EXAFS. XPS and XANES were used to determine U oxidation states. Spectral shifts were obtained at the U 4f 7/2 and U 4f 5/2 binding energies using XPS, and at the uranium M V absorption edge using XANES. The magnitude of the energy shift with oxidation state, and the ability to detect mixed-valent forms make these ideal techniques for determining uranium speciation in wastes subjected to bacterial action. The structure of 1:1 U:citric acid complex in both the aqueous and solid state was determined by EXAFS analysis of hexavalent uranium at the L M absorption edge and suggests the presence of a binuclear complex with a (UO 2 ) 2 (μ,η 2 -citrato) 2 core with a U-U distance of 5.2 angstrom. The influence of Fe on the structure of U-citrate complex was determined by EXAFS and the presence of a binuclear mixed-metal citrate complex with a U-Fe distance of 4.8 angstrom was confirmed. The precipitate resulting from photodegradation of U-citrate complex was identified as an amorphous form of uranium trioxide by XPS and EXAS

Method of manufacturing mixed stock powders for nuclear fuel elements

International Nuclear Information System (INIS)

Hirayama, Satoshi.

1980-01-01

Purpose: To alleviate the limit of the present reactor operating conditions by uniformly mixing an additive to the main content as an uranium dioxide or mixture of the uranium dioxide with plutonium dioxide. Method: A mixed stock powder is obtained by adding an additive of at least two of aluminium oxide, beryllium oxide, calcium oxide, magnesium oxide, silicon oxide, sodium oxide, potassium oxide, phosphorus oxide, titanium oxide and iron oxide to suspension having ammonia water as dispersion medium to start the deposition of precipitation at a step of precipitating ammonium diuranate or plutionium hydroxide of a main content of uranium dioxide or mixture of uranium dioxide and plutonium dioxide and deposited precipitate is calcinated and reduced. (Yoshihara, H.)

Study on the radiotoxicology of enriched uranium

International Nuclear Information System (INIS)

Zhu Shoupeng; Zheng Siying; Wang Guolin; Wang Chongdao; Cao Genfa

1987-12-01

A study on the retentive peculiarity of soluble enriched uranium UO 2 F 2 were observed after iv once or consecutive ip qd x 3d to Wistar male rats. The dynamic retention of radioactivity in the body showed that the enriched uranium UO 2 F 2 was chiefly localized in kidney, and then in skeleton and liver. The radioactivity of the enriched uranium UO 2 F 2 in skeleton rose steadily while the concentratoin in kidney and liver droped. When enriched uranium UO 2 F 2 was accumulated in organism, it caused chromosome aberrations on bone marrow cells. Results indicated that the chromosome aberration rates were elevated when the dose of the enriched uranium UO 2 F 2 was increased, at the same time, the cell division was depressed. Accumulation of insoluble enriched uranium U 3 O 8 in gastrointestinal tract was well described by a two exponential expression. Values of retention estimate for fast component, T 1 = 0.34 d, and for relatively long term component, T 2 = 4.05 d. The deposition of UO 2 F 2 in the intact skin was only 0.16 to 0.18% of the total contaminated UO 2 F 2 . Penetration of the enriched uranium UO 2 F 2 was dominantly increased in abraded skin. This value is about 25 to 32 times as compaired with that in intact skin. Retention of the enriched uranium UO 2 F 2 through abraded skins was dominantly localized in kidney and skeleton

Uranium-mediated electrocatalytic dihydrogen production from water

Science.gov (United States)

Halter, Dominik P.; Heinemann, Frank W.; Bachmann, Julien; Meyer, Karsten

2016-02-01

Depleted uranium is a mildly radioactive waste product that is stockpiled worldwide. The chemical reactivity of uranium complexes is well documented, including the stoichiometric activation of small molecules of biological and industrial interest such as H2O, CO2, CO, or N2 (refs 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11), but catalytic transformations with actinides remain underexplored in comparison to transition-metal catalysis. For reduction of water to H2, complexes of low-valent uranium show the highest potential, but are known to react violently and uncontrollably forming stable bridging oxo or uranyl species. As a result, only a few oxidations of uranium with water have been reported so far; all stoichiometric. Catalytic H2 production, however, requires the reductive recovery of the catalyst via a challenging cleavage of the uranium-bound oxygen-containing ligand. Here we report the electrocatalytic water reduction observed with a trisaryloxide U(III) complex [((Ad,MeArO)3mes)U] (refs 18 and 19)—the first homogeneous uranium catalyst for H2 production from H2O. The catalytic cycle involves rare terminal U(IV)-OH and U(V)=O complexes, which have been isolated, characterized, and proven to be integral parts of the catalytic mechanism. The recognition of uranium compounds as potentially useful catalysts suggests new applications for such light actinides. The development of uranium-based catalysts provides new perspectives on nuclear waste management strategies, by suggesting that mildly radioactive depleted uranium—an abundant waste product of the nuclear power industry—could be a valuable resource.

Inositol hexa-phosphate: a potential chelating agent for uranium

International Nuclear Information System (INIS)

Cebrian, D.; Tapia, A.; Real, A.; Morcillo, M.A.

2007-01-01

Chelation therapy is an optimal method to reduce the radionuclide-related risks. In the case of uranium incorporation, the treatment of choice is so far i.v infusion of a 1.4% sodium bicarbonate solution, but the efficacy has been proved to be not very high. In this study, we examine the efficacy of some substances: bicarbonate, citrate, diethylenetriamine pentaacetic acid (DTPA), ethidronate (EHBP) and inositol hexa-phosphate (phytic acid) to chelate uranium using a test developed by Braun et al. Different concentrations of phytic acid, an abundant component of plant seeds that is widely distributed in animal cells and tissues in substantial levels, were tested and compared to the same concentrations of sodium citrate, bicarbonate, EHBP and DTPA. The results showed a strong affinity of inositol hexa-phosphate for uranium, suggesting that it could be an effective chelating agent for uranium in vivo. (authors)

Reactions of uranium (III) and (IV) compounds with ketones, nitriles and acid chlorides. Towards a use of uranium complexes in organic synthesis

International Nuclear Information System (INIS)

Adam, Raymond

1993-01-01

In this research thesis, the author shows that various organic molecules can be interestingly transformed into uranium complexes with degrees of oxidation of +3 or +4. In a first part, the author describes reactions of carbonyl compounds with the UCl 4 -Na(Hg) reducing system. Then, he addresses reductions of ketones, nitriles and acid chlorides by a uranium (III) complex: Cp 3 U(THF). The third part reports a detailed study of the reduction of ketones by U(BH 4 ) 4 [fr

cis-dioxovanadium(V) and mixed-valence divanadium(IV, V) complexes containing β-diketonate and heterocyclic nitrogen-base ligands

International Nuclear Information System (INIS)

Taguchi, Hiroshi; Isobe, Kiyoshi; Nakamura, Yukio; Kawaguchi, Shinichi

1978-01-01

Diamagnetic dioxovanadium(V) complexes, VO 2 (β-dik)(phen or bpy), were prepared by the direct reactions of VO(β-dik) 2 with 1,10-phenanthroline and 2,2'-bipyridine in dichloromethane under aerobic conditions as well as by two other methods. These compounds were concluded to have a cis configuration on the basis of the IR and Raman data. These complexes are solvolyzed to afford the di-μ-methoxo- or di-μ-hydroxo-divanadium(V) species, and are reduced by hydrogen bromide to the oxovanadium(IV) species in dichloromethane. In methanol instead of dichloromethane, VO(acac) 2 reacted with 2,2'-bipyridine to produce a novel mixed-valence divanadium(IV, V) complex, V 2 O 3 (acac) 3 (bpy), which was revealed by the magnetic, spectral, and polarographic data to be a trans adduct of VO(acac) 2 with VO 2 (acac)(bpy) via an oxide ligand. (auth.)

Fuel/propellant mixing in an open-cycle gas core nuclear rocket engine

International Nuclear Information System (INIS)

Guo, X.; Wehrmeyer, J.A.

1997-01-01

A numerical investigation of the mixing of gaseous uranium and hydrogen inside an open-cycle gas core nuclear rocket engine (spherical geometry) is presented. The gaseous uranium fuel is injected near the centerline of the spherical engine cavity at a constant mass flow rate, and the hydrogen propellant is injected around the periphery of the engine at a five degree angle to the wall, at a constant mass flow rate. The main objective is to seek ways to minimize the mixing of uranium and hydrogen by choosing a suitable injector geometry for the mixing of light and heavy gas streams. Three different uranium inlet areas are presented, and also three different turbulent models (k-var-epsilon model, RNG k-var-epsilon model, and RSM model) are investigated. The commercial CFD code, FLUENT, is used to model the flow field. Uranium mole fraction, axial mass flux, and radial mass flux contours are obtained. copyright 1997 American Institute of Physics

Semi-automated uranium analysis by a modified Davies--Gray procedure

International Nuclear Information System (INIS)

Swanson, G.C.

1977-01-01

To rapidly and reliably determine uranium in fuel materials a semi-automated implementation of the Davies-Gray uranium titration was developed. The Davies-Gray method is essentially a three step procedure. First uranium is reduced quantitatively from +6 valence to +4 valence by excess of iron (II) in strong phosphoric acid in the absence of nitrite. Prior to the uranium reduction nitrite is destroyed by addition of sulfamic acid. In the second step iron (II) is selectively oxidized to iron (III) by nitric acid in the presence of Mo (VI) catalyst. Finally after dilution to reduce phosphate concentration, the uranium is titrated to U (VI) by standard dichromate. The original sluggish colorimetric endpoint determination used by Davies and Gray is seldom used since New Brunswick Laboratory discovered that addition of vanadium (IV) just prior to titration sufficiently improves reaction rate to allow a potentiometric endpoint determination. One of the advantages of the Davies-Gray uranium titration is that it is quite specific for uranium, most common impurity elements do not interfere with the analysis, and specifically high levels of Pu, Th, and Fe are tolerated

Geochemical behavior of uranium mill tailings leachate in the subsurface

International Nuclear Information System (INIS)

Brookins, D.G.

1993-01-01

Leachate generated from surface disposal of acidic uranium mill tailings at Maybell, CO has impacted groundwater quality within the underlying mineralized Browns Park Formation. The extent of groundwater contamination, however, is located directly beneath the tailings impoundment. The milling process consisted of sulfuric acid extraction of uranium from the feed ore by a complex chemical leaching and precipitation process. Tailings leachate at the site contains elevated concentrations of Al, As, Cd, Mo, Ni, NO 3 , Se, U, and other solutes. From column leach tests, the concentrations of contaminants within tailings pore fluid are SO 4 >NH 4 >NO 3 >U>Se>Ni>As>Cd at pH 4.0. The carbonate buffering capacity of the tailings subsoil has decreased because of calcite dissolution in the presence of acidic leachate. Groundwater quality data, mineralogical and microbiological studies, and geochemical modeling suggest that As, NO 3 , Se, U and other solutes are being removed from solution through precipitation, adsorption, and denitrification processes under reducing conditions. Presence of hydrogen sulfide, liquid and gaseous hydrocarbons, dissolved organic, and abundant pyrite within the Browns Park Formations have maintained reducing conditions subjacent to the tailings impoundment. Groundwater is in close equilibrium with coffinite and uraninite, the primary U(IV) minerals extracted from the Browns Parks Formation. Denitrifying bacteria identified in this study catalyze redox reactions involving NO 3 . Subsequently, contaminant distributions of NO 3 decrease 1000 times beneath the tailings impoundment. Applying geochemical and biochemical processes occurring at Maybell provides an excellent model for in situ aquifer restoration programs considered at other uranium tailings and heavy-metal-mixed waste contaminated sites. (author) 4 figs., 4 tabs., 27 refs

Nuclear energy - Uranium dioxide powder and sintered pellets - Determination of oxygen/uranium atomic ratio by the amperometric method. 2. ed.

International Nuclear Information System (INIS)

2007-01-01

This International Standard specifies an analytical method for the determination of the oxygen/uranium atomic ratio in uranium dioxide powder and sintered pellets. The method is applicable to reactor grade samples of hyper-stoichiometric uranium dioxide powder and pellets. The presence of reducing agents or residual organic additives invalidates the procedure. The test sample is dissolved in orthophosphoric acid, which does not oxidize the uranium(IV) from UO 2 molecules. Thus, the uranium(VI) that is present in the dissolved solution is from UO 3 and/or U 3 O 8 molecules only, and is proportional to the excess oxygen in these molecules. The uranium(VI) content of the solution is determined by titration with a previously standardized solution of ammonium iron(II) sulfate hexahydrate in orthophosphoric acid. The end-point of the titration is determined amperometrically using a pair of polarized platinum electrodes. The oxygen/uranium ratio is calculated from the uranium(VI) content. A portion, weighing about 1 g, of the test sample is dissolved in orthophosphoric acid. The dissolution is performed in an atmosphere of nitrogen or carbon dioxide when sintered material is being analysed. When highly sintered material is being analysed, the dissolution is performed at a higher temperature in purified phosphoric acid from which the water has been partly removed. The cooled solution is titrated with an orthophosphoric acid solution of ammonium iron(II) sulfate, which has previously been standardized against potassium dichromate. The end-point of the titration is detected by the sudden increase of current between a pair of polarized platinum electrodes on the addition of an excess of ammonium iron(II) sulfate solution. The paper provides information about scope, principle, reactions, reagents, apparatus, preparation of test sample, procedure (uranium dioxide powder, sintered pellets of uranium dioxide, highly sintered pellets of uranium dioxide and determination

Thermodynamic properties of uranium in gallium–aluminium based alloys

International Nuclear Information System (INIS)

Volkovich, V.A.; Maltsev, D.S.; Yamshchikov, L.F.; Chukin, A.V.; Smolenski, V.V.; Novoselova, A.V.; Osipenko, A.G.

2015-01-01

Activity, activity coefficients and solubility of uranium was determined in gallium-aluminium alloys containing 1.6 (eutectic), 5 and 20 wt.% aluminium. Additionally, activity of uranium was determined in aluminium and Ga–Al alloys containing 0.014–20 wt.% Al. Experiments were performed up to 1073 K. Intermetallic compounds formed in the alloys were characterized by X-ray diffraction. Partial and excess thermodynamic functions of U in the studied alloys were calculated. - Highlights: • Thermodynamics of uranium is determined in Ga–Al alloys of various compositions. • Uranium in the mixed alloys interacts with both components, Ga and Al. • Interaction of U with Al increases with decreasing temperature. • Activity and solubility of uranium depend on Al content in Ga–Al alloys.

Thermodynamic properties of uranium in gallium–aluminium based alloys

Energy Technology Data Exchange (ETDEWEB)

Volkovich, V.A., E-mail: v.a.volkovich@urfu.ru [Department of Rare Metals and Nanomaterials, Institute of Physics and Technology, Ural Federal University, Ekaterinburg, 620002 (Russian Federation); Maltsev, D.S.; Yamshchikov, L.F. [Department of Rare Metals and Nanomaterials, Institute of Physics and Technology, Ural Federal University, Ekaterinburg, 620002 (Russian Federation); Chukin, A.V. [Department of Theoretical Physics and Applied Mathematics, Institute of Physics and Technology, Ural Federal University, Ekaterinburg, 620002 (Russian Federation); Smolenski, V.V.; Novoselova, A.V. [Institute of High-Temperature Electrochemistry UD RAS, Ekaterinburg, 620137 (Russian Federation); Osipenko, A.G. [JSC “State Scientific Centre - Research Institute of Atomic Reactors”, Dimitrovgrad, 433510 (Russian Federation)

2015-10-15

Activity, activity coefficients and solubility of uranium was determined in gallium-aluminium alloys containing 1.6 (eutectic), 5 and 20 wt.% aluminium. Additionally, activity of uranium was determined in aluminium and Ga–Al alloys containing 0.014–20 wt.% Al. Experiments were performed up to 1073 K. Intermetallic compounds formed in the alloys were characterized by X-ray diffraction. Partial and excess thermodynamic functions of U in the studied alloys were calculated. - Highlights: • Thermodynamics of uranium is determined in Ga–Al alloys of various compositions. • Uranium in the mixed alloys interacts with both components, Ga and Al. • Interaction of U with Al increases with decreasing temperature. • Activity and solubility of uranium depend on Al content in Ga–Al alloys.

Uranium 234U and 238U isotopes in the southern Baltic environment

International Nuclear Information System (INIS)

Borylo, A.; Skwarzec, B.

2002-01-01

The concentration and distribution of uranium in water and sediment of selected basins of the southern Baltic Sea have been analysed. It was observed that the concentration of uranium in sediments increases with core depth. This is probably connected to diffusion processes from sediments to water through interstitial water where uranium concentration is much higher than in bottom water. The measurements of 234 U/ 238 U activity ratios indicate that sedimentation of terrigenic material and transport through Vistula river are the major sources of uranium in sediments of the southern Baltic Sea. Estimation of the 234 U/ 238 U ratios in reduction areas of the Baltic Deep and the Bornholm Deep suggest that the processes of reduction of U(VI) to U(IV) and of removal of authogenic uranium from seawater to sediments do not play major roles in the Gdansk Deep. (author)

Irradiation behaviour of mixed uranium-plutonium carbides, nitrides and carbonitrides; Comportement a l'irradiation de carbures, nitrures et carbonitrures mixtes d'uranium et de plutonium

Energy Technology Data Exchange (ETDEWEB)

Mikailoff, H; Mustelier, J P; Bloch, J; Leclere, J; Hayet, L [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1967-07-01

In the framework of the research program of fast reactor fuels two irradiation experiments have been carried out on mixed uranium-plutonium carbides, nitrides and carbo-nitrides. In the first experiment carried out with thermal neutrons, the fuel consisted of sintered pellets sheathed in a stainless steel can with a small gap filled with helium. There were three mixed mono-carbide samples and the maximum linear power was 715 W/cm. After a burn-up slightly lower than 20000 MW day/tonne, a swelling of the fuel which had ruptured the cans was observed. In the second experiment carried out in the BR2 reactor with epithermal neutrons, the samples consisted of sintered pellets sodium bonded in a stainless steel tube. There were three samples containing different fuels and the linear power varies between 1130 and 1820 W/cm. Post-irradiation examination after a maximal burn-up of 1550 MW day/tonne showed that the behaviour of the three fuel elements was satisfactory. (authors) [French] Dans le cadre du programme d'etude des conibustiles pour reacteurs rapides, on a realise deux experiences d'irradiation de carbures, nitrures et carbonitrures mixtes d'uranium et de plutonium. Dans la premiere experience, faite en neutrons thermiques, le combustible etait constitue de,pastilles frittees gainees dans un tube d'acier inoxydable avec un faible jeu rempli d'helium. Il y avait trois echantillons de monocarbures mixtes, et la puissance lineaire maximale etait de 715 W/cm. Apres un taux de combustion legerement inferieur a 20 000 MWj/t, on a observe un gonflement des combustible qui a provoque, la rupture des gaines. Pans la seconde experience, realisee dans le reacteur BR2 en neutrons epithermiques, les echantillons etaient constitues de pastilles frittees gainees dans un tube d'acier avec un joint sodium. Il y avait trois echantillons contenant des combustibles differents, et la puissance lineaire variait de 1130 a 1820 W/cm. Les examens apres irradiation a un taux maximal de

Adaptation of U(IV) reductant to Savannah River Plant Purex processes

International Nuclear Information System (INIS)

Orebaugh, E.G.

1986-04-01

Partitioning of uranium and plutonium in the Purex process requires the reduction of the extracted Pu(IV) to the less extractable Pu(III). This valence adjustment at SRP has historically been performed by the addition of ferrous ion, which eventually constitutes a major component of high-level waste solids requiring costly permanent disposal. Uranous nitrate, U(IV), is a kinetically fast reductant which may be substituted for Fe(II) without contributing to waste solids. This report documents U(IV) flowsheet development in the miniature mixer-settler equipment at SRL and provides an insight into the mechanisms responsible for the successful direct substitution of U(IV) for Fe(II) in 1B bank extractant. U(IV) will be the reductant of choice when its fast reduction kinetics are required in centrifugal-contactor-based processing. The flowsheets investigated here should transfer to such equipment with minimal modifications

Kinetics of the reduction of plutonium(IV) by hydroxyurea, a novel salt-free agent

International Nuclear Information System (INIS)

Zhu Zhaowu; He Jianyu; Zhang Zefu; Zhang Yu; Zheng Weifang

2004-01-01

The kinetics of the reduction of plutonium(IV) by hydroxyurea (HU), a novel salt free reductant, in nitric acid solutions has been studied. The observed reaction rate can be expressed as: -d[Pu(IV)]/dt=k 0 [Pu(IV)] 2 [HU]/[H + ] 0.9 , where k 0 = 5853 ± 363 (l 1.1 x mol -1.1 x s -1 ) at t = 13 deg C. The activation energy is about 81.2 kJ/mol. It was also shows that uranium(VI) has no appreciable influence on the reaction rate. Compared with other organic reductants our experiments indicate that HU is a very fast reductant for plutonium(IV). (author)

Anomalous isotope effects in the U(IV)-U(VI) exchange system

International Nuclear Information System (INIS)

Fujii, Yasuhiko; Nomura, Masao; Okamoto, Makoto; Onitsuka, Hatsuki; Nakanishi, Takashi.

1992-01-01

In previous papers, the enrichment of 236 U in the U(IV) - U(VI) chemical exchange system was found to be significantly smaller than the value estimated by the normal mass dependence enrichment of 235 U. Further experiments have been carried out in the present work to confirm the strange phenomenon of the isotopic anomaly in uranium enrichment. The results have indicated that the separation coefficient of 236 U is the same value as one previously reported. To confirm the anomaly of uranium isotope separation, α-ray spectrometry was implemented to check the enrichment behavior of 234 U. Although no theoretical explanation is given for the isotopic anomaly, this is favorable phenomenon for the re-enrichment of recycled uranium which contains isotopes 232 U and 236 U. (author)

The low enriched uranium fuel cycle in Ontario

International Nuclear Information System (INIS)

Archinoff, G.H.

1979-02-01

Six fuel-cycle strategies for use in CANDU reactors are examined in terms of their uranium-conserving properties and their ease of commercialization for three assumed growth rates of installed nuclear capacity in Ontario. The fuel cycle strategies considered assume the continued use of the natural uranium cycle up to the mid-1990's. At that time, the low-enriched uranium (LEU) cycle is gradually introduced into the existing power generation grid. In the mid-2020's one of four advanced cycles is introduced. The advanced cycles considered are: mixed oxide, intermediate burn-up thorium (Pu topping), intermediate burn-up thorium (U topping), and LMFBR. For comparison purposes an all natural uranium strategy and a natural uranium-LEU strategy (with no advanced cycle) are also included. None of the strategies emerges as a clear, overall best choice. (LL)

PWR core design, neutronics evaluation and fuel cycle analysis for thorium-uranium breeding recycle

International Nuclear Information System (INIS)

Bi, G.; Liu, C.; Si, S.

2012-01-01

This paper was focused on core design, neutronics evaluation and fuel cycle analysis for Thorium-Uranium Breeding Recycle in current PWRs, without any major change to the fuel lattice and the core internals, but substituting the UOX pellet with Thorium-based pellet. The fuel cycle analysis indicates that Thorium-Uranium Breeding Recycle is technically feasible in current PWRs. A 4-loop, 193-assembly PWR core utilizing 17 x 17 fuel assemblies (FAs) was taken as the model core. Two mixed cores were investigated respectively loaded with mixed reactor grade Plutonium-Thorium (PuThOX) FAs and mixed reactor grade 233 U-Thorium (U 3 ThOX) FAs on the basis of reference full Uranium oxide (UOX) equilibrium-cycle core. The UOX/PuThOX mixed core consists of 121 UOX FAs and 72 PuThOX FAs. The reactor grade 233 U extracted from burnt PuThOX fuel was used to fabrication of U 3 ThOX for starting Thorium-. Uranium breeding recycle. In UOX/U 3 ThOX mixed core, the well designed U 3 ThOX FAs with 1.94 w/o fissile uranium (mainly 233 U) were located on the periphery of core as a blanket region. U 3 ThOX FAs remained in-core for 6 cycles with the discharged burnup achieving 28 GWD/tHM. Compared with initially loading, the fissile material inventory in U 3 ThOX fuel has increased by 7% via 1-year cooling after discharge. 157 UOX fuel assemblies were located in the inner of UOX/U 3 ThOX mixed core refueling with 64 FAs at each cycle. The designed UOX/PuThOX and UOX/U 3 ThOX mixed core satisfied related nuclear design criteria. The full core performance analyses have shown that mixed core with PuThOX loading has similar impacts as MOX on several neutronic characteristic parameters, such as reduced differential boron worth, higher critical boron concentration, more negative moderator temperature coefficient, reduced control rod worth, reduced shutdown margin, etc.; while mixed core with U 3 ThOX loading on the periphery of core has no visible impacts on neutronic characteristics compared

A computer controlled potentiometric titrator for quantitative determination of uranium

International Nuclear Information System (INIS)

Verdingh, V.; Michiels, A.

1988-01-01

The modified Davies and Gray methods is frequently used for the potentiometric titration of uranium. It is based upon the reduction of U(VI) to U(IV) with a reductant (e.g. Fe ++ ) followed by a selective oxidation of the excess of reductant and subsequent titration of U(IV) with potassium dichromate (K 2 Cr 2 O 7 ). Interference from other elements is low, but the method is rather cumbersome due to the number of reactants to be added before the titration is started. The timing of these additions also plays a role. In order to render the titration less dependent on human factors and with the aim of reaching high reproducibility, a computer controlled system has been designed and set-up. Reagents are added by five computer controlled burettes. A program allows the choice of volumes and waiting times, and commands the start of the final titration which is followed by the microprocessor of the automatic potentiometric titrator. In this way a routine uranium titration can be completed in about twelve minutes. Reproducibilities of the order of ±15% are achievable in routine operation. For high precision work, the titrator is used as an end-point detector. Titrant is added manually by mass, so as to react with > 99% of the uranium. The residual uranium is then titrated automatically by colume with diluted titrant. The precision can be improved by a factor of approximately ten. (orig.)

Separation and recovery of uranium ore by chlorinating, chelate resin and molten salt treatment

International Nuclear Information System (INIS)

Taki, Tomohiro

2000-12-01

Three fundamental researches of separation and recovery of uranium from uranium ore are reported in this paper. Three methods used the chloride pyrometallurgy, sodium containing molten salts and chelate resin. When uranium ore is mixed with activated carbon and reacted for one hour under the mixed gas of chlorine and oxygen at 950 C, more than 90% uranium volatilized and vaporization of aluminum, silicone and phosphorus were controlled. The best activated carbon was brown coal because it was able to control the large range of oxygen concentration. By blowing oxygen into the molten sodium hydroxide, the elution rate of uranium attained to about 95% and a few percent of uranium was remained in the residue. On the uranium ore of unconformity-related uranium deposits, a separation method of uranium, molybdenum, nickel and phosphorus from the sulfuric acid elusion solution with U, Ni, As, Mo, Fe and Al was developed. Methylene phosphonic acid type chelate resin (RCSP) adsorbed Mo and U, and then 100 % Mo was eluted by sodium acetate solution and about 100% U by sodium carbonate solution. Ni and As in the passing solution were recovered by imino-diacetic acid type chelate resin and iron hydroxide, respectively. (S.Y.)

DUPoly process for treatment of depleted uranium and production of beneficial end products

International Nuclear Information System (INIS)

Kalb, P.D.; Adams, J.W.; Lageraaen, P.R.; Cooley, C.R.

2000-01-01

The present invention provides a process of encapsulating depleted uranium by forming a homogeneous mixture of depleted uranium and molten virgin or recycled thermoplastic polymer into desired shapes. Separate streams of depleted uranium and virgin or recycled thermoplastic polymer are simultaneously subjected to heating and mixing conditions. The heating and mixing conditions are provided by a thermokinetic mixer, continuous mixer or an extruder and preferably by a thermokinetic mixer or continuous mixer followed by an extruder. The resulting DUPoly shapes can be molded into radiation shielding material or can be used as counter weights for use in airplanes, helicopters, ships, missiles, armor or projectiles

Separation and purification of uranium by ion exchange on stannic phosphate

International Nuclear Information System (INIS)

Mayankutty, P.C.; Nadkarni, M.N.; Venkateswarlu, K.S.

1977-01-01

Exchange of uranium, plutonium and some fission product elements was investigated on stannic phosphate (SnP) exchanger from nitric acid solutions. Batch equilibration studies exhibited stronger absorption of plutonium (IV) and some of the fission products on the exchanger than uranium. This indicated the possibility of separation and purification of uranium from plutonium and fission products. Breakthrough studies were carried out to determine the effects of flow-rates and uranium, plutonium and free nitric acid concentrations in the feed to establish the optimum conditions for this separation. Several reagents were also tested to find suitable eluting agents to desorb plutonium from the exchanger. The results indicate that traces of plutonium and fission products present as impurities in the uranium product of the purex process stream can be removed by ion exchange method using SnP. 1 M nitric acid solution containing low concentrations of reducing agents such as ferrous sulfamate or ascorbic acid was found to be an effective eluting agent for plutonium. (author)

The possibility of the mixed valence state in the uranium intermetallic compounds: UCoGa5, U2Ru2Sn and U2RuGa8

International Nuclear Information System (INIS)

Troc, Robert

2007-01-01

The mixed valence (MV) phenomenon has been observed so far in a large number of various compounds but containing only lanthanides. These properties are usually associated with the mixing of the localised f-state and the band states. The usual valence state for magnetic uranium intermetallics is the trivalent state 5f 3 or hybridised 5f 2 6d 1 , both are nearly degenerate in energy and can compete for a stability of the compound. In some cases a gain in an energy minimum may be achieved by very fast fluctuating between these two states with a time of 10 -14 s, which does not allow to yield the ordered state even if the exchange interactions (favourite the U-U distances) would be able for that. The latter cases seem to concern the described here intermetallics: one ternary compound based on Co, UCoGa 5 , and the two uranium ternary compounds based on Ru, namely U 2 Ru 2 Sn and U 2 RuGa 8 which all crystallize in a tetragonal unit cell. All these compounds show a maximum in their temperature dependences of the magnetic susceptibility measured along and perpendicular to the c-axis. Such a behaviour, which is reminiscent of a number of Ce (Sm, Eu) and Yb compounds for which χ(T) has in the past been considered by Sales and Wohlleben (SW) by applying their ICF model or by Lawrance et al. following their scaling procedure. It turned out that these phenomenological models can also be applied to the considered here two Ru-based uranium ternaries from which some reliable energy parameters could be found. In order to further support the mixing valence scenario for the first such cases in uranium compounds presented here, the transport and thermodynamic properties are also discussed. However, some of the most important results confirming the MV state, e.g., in U 2 RuGa 8 , has recently been achieved from the inelastic neutron scattering performed in the Rutherford Appleton Laboratory on the ISIS facility. From these measurements a characteristic gap of 60 meV has been

New Technique for Speciation of Uranium in Sediments Following Acetate-Stimulated Bioremediation

Energy Technology Data Exchange (ETDEWEB)

2011-06-22

Acetate-stimulated bioremediation is a promising new technique for sequestering toxic uranium contamination from groundwater. The speciation of uranium in sediments after such bioremediation attempts remains unknown as a result of low uranium concentration, and is important to analyzing the stability of sequestered uranium. A new technique was developed for investigating the oxidation state and local molecular structure of uranium from field site sediments using X-Ray Absorption Spectroscopy (XAS), and was implemented at the site of a former uranium mill in Rifle, CO. Glass columns filled with bioactive Rifle sediments were deployed in wells in the contaminated Rifle aquifer and amended with a hexavalent uranium (U(VI)) stock solution to increase uranium concentration while maintaining field conditions. This sediment was harvested and XAS was utilized to analyze the oxidation state and local molecular structure of the uranium in sediment samples. Extended X-Ray Absorption Fine Structure (EXAFS) data was collected and compared to known uranium spectra to determine the local molecular structure of the uranium in the sediment. Fitting was used to determine that the field site sediments did not contain uraninite (UO{sub 2}), indicating that models based on bioreduction using pure bacterial cultures are not accurate for bioremediation in the field. Stability tests on the monomeric tetravalent uranium (U(IV)) produced by bioremediation are needed in order to assess the efficacy of acetate-stimulation bioremediation.

The oxidation of uranium(IV) ions by nitrous acid in 30% tri-butyl phosphate

International Nuclear Information System (INIS)

Koltunov, V.S.; Marchenko, V.I.; Savilova, O.A.; Dvoeglazov, K.N.; Taylor, R.J.

2004-01-01

The kinetics of the oxidation of U(IV) ions by nitrous acid in a 30% TBP solution have been determined. The rate equation was found to be: - d[U(IV)] / dt = k 2a [U(IV)][HNO 2 ][HNO 3 ][H 2 O] / [HNO 3 ] 2 + β 3 [HNO 3 ][H 2 O] + β 4 [H 2 O] 2 , where, k 2a = 0.405 ± 0.055 M -1 min -1 at 55 C (β 3 ∼ 0.08; β 4 ∼ 0.007) and the activation energy was E = 112 ± 17 kJ mol -1 . The reaction mechanism appeared to involve interaction with the 1 st hydrolysis product of U(IV)-UOH 3+ . The data is compared with a previous study of the nitric acid oxidation of U(IV) in 30% TBP. This reaction is autocatalytic due to the formation of nitrous acid during the reaction. The kinetics of the decomposition of HNO 2 in 30% TBP (in the absence of U(IV)) have also been reported. (orig.)

Study of the oxidation state of arsenic and uranium in individual particles from uranium mine tailings, Hungary

International Nuclear Information System (INIS)

Alsecz, A.; Osan, J.; Palfalvi, J.; Torok, Sz.; Sajo, I.; Mathe, Z.; Simon, R.; Falkenberg, G.

2007-01-01

Uranium ore mining and milling have been terminated in the Mecsek Mountains (southwest Hungary) in 1997. Mine tailings ponds are located between two important water bases, which are resources of the drinking water of the city of Pecs and the neighbouring villages. The average U concentration of the tailings material is 71.73 μg/g, but it is inhomogeneous. Some microscopic particles contain orders of magnitude more U than the rest of the tailings material. Other potentially toxic elements are As and Pb of which chemical state is important to estimate mobility, because in mobile form they can risk the water basis and the public health. Individual U-rich particles were selected with solid state nuclear track detector (SSNTD) and after localisation the particles were investigated by synchrotron radiation based microanalytical techniques. The distribution of elements over the particles was studied by micro beam X-ray fluorescence (μ-XRF) and the oxidation state of uranium and arsenic was determined by micro X-ray absorption near edge structure (μ-XANES) spectroscopy. Some of the measured U-rich particles were chosen for studying the heterogeneity with μ-XRF tomography. Arsenic was present mainly in As(V) and uranium in U(VI) form in the original uranium ore particles, but in the mine tailings samples uranium was present mainly in the less mobile U(IV) form. Correlation was found between the oxidation state of As and U in the same analyzed particles. These results suggest that dissolution of uranium is not expected in short term period. (authors)

Evaluating chemical extraction techniques for the determination of uranium oxidation state in reduced aquifer sediments

Science.gov (United States)

Stoliker, Deborah L.; Campbell, Kate M.; Fox, Patricia M.; Singer, David M.; Kaviani, Nazila; Carey, Minna; Peck, Nicole E.; Barger, John R.; Kent, Douglas B.; Davis, James A.

2013-01-01

Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).

Determination of uranium in liquid samples

International Nuclear Information System (INIS)

Macefat, Martina R.; Grahek, Zeljko; Ivsic, Astrid G.

2008-01-01

Full text: Uranium is a natural occurring radionuclide and the first member of natural radioactive chains which makes its determination in natural materials interesting from geochemical and radioecological aspect. It can be quantitatively determined as element and/or its radioisotopes by different spectrometric methods (ICP-MS, spectrophotometry, alpha spectrometry). It is necessary to develop inexpensive, rapid and sensitive methods for the routine analysis. Therefore, in this paper, development of a new method for the isolation of uranium from liquid samples and subsequent determination by spectrophotometry and ICP-MS will be described. It is possible to isolate uranium from drinking and seawater using extraction chromatography or mixed solvent ion exchange. Uranium can be strongly bound on the TRU extraction chromatographic resin from nitric acid (chemical recovery is 100%) and can be separated from other interfering elements, while separation from thorium, which can be also strongly bound on this resin, is possible with hydrochloric acid. It is also possible to separate uranium from thorium on the anion exchanger Amberlite CG-400 (NO 3 - form) because uranium is much more weakly bound on this exchanger from alcoholic solutions of nitric acid. After the separation uranium is determined by ICP-MS and by spectrophotometric method with arsenazo III (λ max =652 nm). Developed method enables selection of the optimal mode of isolation for the given purposes. (author)

Amine extraction of lead(II) and zirconium(IV) with succinate media

International Nuclear Information System (INIS)

Mahamuni, S.V.; Mane, C.P.; Sargar, B.M.; Rajmane, M.M.; Anuse, M.A.

2004-01-01

Lead is an important constituent of various alloys, which are in increasing demand in manufacture of batteries and nuclear shielding while the use of zirconium in nuclear power plants as entirely cladding uranium fuel is most important. This study was carried out to optimize the extraction conditions for Pb(II) and zirconium(IV)

A Preliminary Study on the Reuse of the Recovered Uranium from the Spent CANDU Fuel Using Pyroprocessing

International Nuclear Information System (INIS)

Park, C. J.; Na, S. H.; Yang, J. H.; Kang, K. H.; Lee, J. W.

2009-01-01

During the pyroprocessing, most of the uranium is gathered in metallic form around a solid cathode during an electro-refining process, which is composed of about 94 weight percent of the spent fuel. In the previous study, a feasibility study has been done to reuse the recovered uranium for the CANDU reactor fuel following the traditional DUPIC (direct use of spent pressurized water reactor fuel into CANDU reactor) fuel fabrication process. However, the weight percent of U-235 in the recovered uranium is about 1 wt% and it is sufficiently re-utilized in a heavy water reactor which uses a natural uranium fuel. The reuse of recovered uranium will bring not only a huge economic profit and saving of uranium resources but also an alleviation of the burden on the management and the disposal of the spent fuel. The research on recycling of recovered uranium was carried out 10 years ago and most of the recovered uranium was assumed to be imported from abroad at that time. The preliminary results showed there is the sufficient possibility to recycle recovered uranium in terms of a reactor's characteristics as well as the fuel performance. However, the spent CANDU fuel is another issue in the storage and disposal problem. At present, most countries are considering that the spent CANDU fuel is disposed directly due to the low enrichment (∼0.5 wt%) of the discharge fissile content and lots of fission products. If mixing the spent CANDU fuel and the spent PWR fuel, the estimated uranium fissile enrichment will be about 0.6 wt% ∼ 1.0 wt% depending on the mixing ratio, which is sufficiently reusable in a CANDU reactor. Therefore, this paper deals with a feasibility study on the recovered uranium of the mixed spent fuel from the pyroprocessing. With the various mixing ratios between the PWR spent fuel and the CANDU spent fuel, a reactor characteristics including the safety parameters of the CANDU reactor was evaluated

Improved fluorimetric measurement of uranium uptake and distribution in spring wheat (Triticum aestivum L.)

Energy Technology Data Exchange (ETDEWEB)

Borcia, Catalin [' ' Alexandru Ioan Cuza' ' Univ., Iasi (Romania). Dept. of Physics; Popa, Karin; Cecal, Alexandru [' ' Alexandru Ioan Cuza' ' Univ., Iasi (Romania). Dept. of Chemistry; Murariu, Manuela [' ' Petru Poni' ' Institute of Macromolecular Chemistry, Iasi (Romania)

2016-08-01

Uranium uptake and (radio)toxicity was tested on spring wheat (Triticum aestivum L.) in a laboratory study using differently concentrated uranium nitrate solutions. Within these experiments, two analytical assays of uranium were comparatively tested: a fast and improved fluorimetric assay and the classical colorimetric (U(IV)-arsenazo(III) complexation) one. During the germination, the wheat seeds and plantlets supported well the uranium solutions of treatment within the entire concentration range (1 x 10{sup -4} -5 x 10{sup -3} M). Uranium proved to be non (radio)toxic to wheat as compared with other natural and anthropogenic radiocations, probably because its uptake by spring wheat during the germination is low. Indeed, only a small fraction of uranium administered was located within the roots, whereas the uranium content of the stems was negligible. A high correlation between the results obtained by two analytical methods was found. However, the fluorimetric assay proved to be more reliable and fast, and accurate.

Microbial transformation of uranium in wastes

International Nuclear Information System (INIS)

Francis, A.J.; Dodge, C.J.; Gillow, J.B.; Cline, J.E.

1989-01-01

Contamination of soils, water, and sediments by radionuclides and toxic metals from the disposal of uranium processing wastes is a major national concern. Although much is known about the physico- chemical aspects of U, we have little information on the effects of aerobic and anaerobic microbial activities on the mobilization or immobilization of U and other toxic metals in mixed wastes. In order to understand the mechanisms of microbial transformations of uranium, we examined a contaminated pond sediment and a sludge sample from the uranium processing facility at Y-12 Plant, Oak Ridge, TN. The uranium concentration in the sediment and sludge samples was 923 and 3080 ug/g dry wt, respectively. In addition to U, the sediment and sludge samples contained high levels of toxic metals such as Cd, Cr, Cu, Hg, Pb, Ni, and Zn. The association of uranium with the various mineral fractions of the sediment and sludge was determined by selective chemical extraction techniques. Uranium was associated to varying degrees with the exchangeable carbonate, iron oxide, organic, and inert fractions in both samples. Initial results in samples amended with carbon and nitrogen indicate immobilization of U due to enhanced indigenous microbial activity under anaerobic conditions. 23 refs., 4 figs., 5 tabs

Trinuclear Schiff base complexes with uranium(V) and copper(II) or zinc(II) ions

Energy Technology Data Exchange (ETDEWEB)

Salmon, L.; Thuery, P.; Ephritikhine, M. [CEA Saclay, DSM, DRECAM, Serv Chim Mol, Lab Claude Frejacques, CNRS URA 331, F-91191 Gif Sur Yvette, (France)

2007-07-01

Treatment of the uranium(IV) complexes [{l_brace}ML{sup 1}(py){r_brace}{sub 2}U(IV)] (M = Cu, Zn; L{sup 1} = N, N'-bis(3-hydroxy-salicylidene)-1,3-propane-diamine) with silver nitrate in pyridine led to the formation of the corresponding cationic uranium(V) species which were found to be thermally unstable and were converted back into the parent U(IV) complexes; no electron transfer was observed in solution between the U(IV) and U(V) compounds. In the crystals of [{l_brace}ML{sup 1}(py){r_brace}{sub 2}U(IV)][{l_brace}ML{sup 1}(py){r_brace}{sub 2}U(V)][NO{sub 3}], the neutral U(IV) and cationic U(V) species are clearly identified by the distinct U-O distances. Similar reaction of [{l_brace}ZnL{sup 2}(py){r_brace}{sub 2}U(IV)] [L{sup 2} N,N'-bis(3-hydroxy-salicylidene)-1,4-butane-diamine] with AgNO{sub 3} gave crystals of [{l_brace}ZnL{sup 2}(py){r_brace}U(V){l_brace}ZnL{sup 2}(py){sub 2}{r_brace}][NO{sub 3}] but the copper counterpart was not isolated. Crystals of [{l_brace}ZnL{sup 1}(py){r_brace}{sub 2}U(V)][OTf].THF (OTf = OSO{sub 2}CF{sub 3}) were obtained fortuitously from the reaction of [Zn(H{sub 2}L{sup 1})] and U(OTf){sub 3}. (authors)

Post-irradiation examinations of uranium-plutonium mixed nitride fuel irradiated in JMTR (89F-3A capsule)

International Nuclear Information System (INIS)

Iwai, Takashi; Nakajima, Kunihisa; Kikuchi, Hironobu; Arai, Yasuo; Kimura, Yasuhiko; Nagashima, Hisao; Sekita, Noriaki

2000-03-01

Two helium-bonded fuel pins filled with uranium-plutonium mixed nitride pellets were encapsulated in 89F-3A and irradiated in JMTR up to 5.5% FIMA at a maximum linear power of 73 kW/m. The capsule cooled for ∼5 months was transported to Reactor Fuel Examination Facility and subjected to non-destructive and destructive post irradiation examinations. Any failure was not observed in the irradiated fuel pins. Very low fission gas release rate of about 2 ∼ 3% was observed, while the diametric increase of fuel pin was limited to ∼0.4% at the position of maximum reading. The inner surface of cladding tube did not show any signs of chemical interaction with fuel pellet. (author)

Distribution of uranium in marine sediments

International Nuclear Information System (INIS)

Ordonez R, E.; Ramirez T, J.J.; Lopez M, J.; Aspiazu, J.; Ruiz F, A.C.; Valero C, N.

2008-01-01

The marine sediments obtained by means of a sampling nucleus in the Gulf of Tehuantepec, Mexico, they have been object of crystallographic and morphological characterization. The PIXE analysis of some samples in study is shown. The normal methodology to carry out the alpha spectroscopy indicates that the sample should be dissolved, but due to the nature of the marine sediments, it thinks about the necessity to make a fractional separation of the sample components. In each stratum of the profile it separates the organic part and the mineral to recover the uranium. It was observed that in the organic phase, the uranium is in two oxidation states (IV and Vl), being necessary the radiochemical separation with a liquid/liquid column chromatographic that uses the di-2-ethyl hexyl phosphoric acid as stationary phase. The uranium compounds extracts are electrodeposited in fine layers on stainless steel disks to carry out the analysis by alpha spectroscopy. The spectroscopic analysis of the uranium indicates us that for each stratum one has a difference marked in the quotient of activities of 234 U/ 238 U that depends on the nature of the studied fraction. These results give us a clear idea about how it is presented the effect of the uranium migration and other radioelements in the biosphere, with what we can determine which are the conditions in that these have their maximum mobility and to know their diffusion patterns in the different media studied. (Author)

Competing retention pathways of uranium upon reaction with Fe(II)

Science.gov (United States)

Massey, Michael S.; Lezama-Pacheco, Juan S.; Jones, Morris E.; Ilton, Eugene S.; Cerrato, José M.; Bargar, John R.; Fendorf, Scott

2014-10-01

Biogeochemical retention processes, including adsorption, reductive precipitation, and incorporation into host minerals, are important in contaminant transport, remediation, and geologic deposition of uranium. Recent work has shown that U can become incorporated into iron (hydr)oxide minerals, with a key pathway arising from Fe(II)-induced transformation of ferrihydrite, (Fe(OH)3·nH2O) to goethite (α-FeO(OH)); this is a possible U retention mechanism in soils and sediments. Several key questions, however, remain unanswered regarding U incorporation into iron (hydr)oxides and this pathway's contribution to U retention, including: (i) the competitiveness of U incorporation versus reduction to U(IV) and subsequent precipitation of UO2; (ii) the oxidation state of incorporated U; (iii) the effects of uranyl aqueous speciation on U incorporation; and, (iv) the mechanism of U incorporation. Here we use a series of batch reactions conducted at pH ∼7, [U(VI)] from 1 to 170 μM, [Fe(II)] from 0 to 3 mM, and [Ca] at 0 or 4 mM coupled with spectroscopic examination of reaction products of Fe(II)-induced ferrihydrite transformation to address these outstanding questions. Uranium retention pathways were identified and quantified using extended X-ray absorption fine structure (EXAFS) spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. Analysis of EXAFS spectra showed that 14-89% of total U was incorporated into goethite, upon reaction with Fe(II) and ferrihydrite. Uranium incorporation was a particularly dominant retention pathway at U concentrations ⩽50 μM when either uranyl-carbonato or calcium-uranyl-carbonato complexes were dominant, accounting for 64-89% of total U. With increasing U(VI) and Fe(II) concentrations, U(VI) reduction to U(IV) became more prevalent, but U incorporation remained a functioning retention pathway. These findings highlight the potential importance of U(V) incorporation within iron

Uranium fixation by mineralization at the redox front

International Nuclear Information System (INIS)

Isobe, Hiroshi

1998-01-01

The behavior of actinide elements including uranium in geomedia is controlled by redox conditions. Under the oxidized conditions, uranium forms uranyl ion (UO 2 2+ ) and its complexes, and dissolves in ground water. Under the reduced conditions, U(IV) has much lower solubility than uranyl ion. In the Koongarra uranium deposit, Australia, lead-bearing uraninite, uranyl lead oxide and uranyl silicate minerals occur in the unweathered, primary ore zone, and uranyl phosphate minerals occur in the weathered, secondary ore zone. Between unweathered and weathered zones, the transition zone exists as a redox front. In the transition zone, graphite and sulfide minerals react as reducing agents for species dissolved in ground water. By SEM, spherical grains of uraninite were observed in veins with graphite. Pyrite had coffinite rim with crystals of uraninite. Calculation based on the ground water chemistry and hydrology at Koongarra shows that the uranium in the transition zone may be fixed from the ground water. In the Koongarra transition zone, recent mineralization of uranium by reduction takes place. Mineralization is much stronger fixation mechanism than adsorption on clay minerals. Pyrite in the buffer materials of possible radioactive waste repositories can fix radionuclides in oxidized ground water by mineralization with reducing reactions. (author)

Uranium and nuclear market, the horizon post-Fukushima

International Nuclear Information System (INIS)

Lelièvre, F.

2014-01-01

Post-Fukushima, most countries have confirmed the importance of nuclear in their energy mix. We are seeing a level of new reactor construction unparalleled in decades with 61 nuclear power plants under construction and 5 plants under completion around the world. Global nuclear capacity is expected to increase by 50% over the next two decades. And more reactors mean more demand for uranium. However, uranium industry is currently grappling with near-term challenges, particularly in the form of depressed uranium prices. Recently several uranium producers announced production delays or cancellations in response to low prices, including major suppliers. As the current price levels, including long-term prices, are not sufficient to stimulate new production, future supplies are in question due to the long-lead nature of uranium mine development. Despite the near- to medium-term issues of our industry, the fundamentals of the uranium market remain strong over the long term - and these are the drivers of the Areva’s mining growth strategy over the coming years. (author)

Uranium in surficial deposits and waters at Palmottu

International Nuclear Information System (INIS)

Ahonen, L.; Blomqvist, R.; Ervanne, H.; Suksi, J.; Jaakkola, T.

1994-01-01

Occurrence of uranium in surficial formations in the vicinity of an underground U deposit was studied. Several water samples from the Lake Palmottu and nearby springs, three lake sediment cores and three peat cores were collected for the study. Uranium concentrations in the water samples varied from 1.4 to 6.9 mBq/l, reflecting the average concentration of near-surface waters in Finland. In some samples, however, the 234 U/ 238 U activity ratio and water chemistry suggest a partial mixing with deeper groundwaters. In the lake sediments, uranium concentrations increases from 53 Bq/kg in surface layer to five fold in the bottom layers deposited 9000 years ago. In peat cores large variations in uranium concentrations can be observed: from tens of Bq/kg to over 20 kBq/kg of peat ash. The large variation also in the 234 U/ 238 U activity ratio, from 0.79 to l.91, tends to indicate uranium migration to the peat from more than one uranium source. (orig.) (19 refs., 5 figs., 1 tab.)

A coalescence model for uranium exploration

International Nuclear Information System (INIS)

Stuart-Williams, V.; Taylor, C.M.

1983-01-01

Uranium mineralization was found in the Pristerognathus-Diictodon Assemblage Zone of the Teekloof Formation, Beaufort Group, west of Beaufort West, Cape Province, South Africa. All the anomalies can be related to a single mineralization model. Mineralization is found at the termination of a silt parting between two coalescing sandstones and lies in the lower sandstone as an inclined zone dipping downflow from the termination of the silt parting. The existence of primary Eh-pH gradient is indicated by a uranium-molybdenum zonation, the molybdenum lying above the uranium mineralization. The upper sandstone was an oxidizing fluvial channel in an arid environment through which uranyl carbonate was being transported in solution. Carbonaceous material undergoing anaerobic bacterial breakdown generated a weakly reducing fluid in the lower sandstone. Carbonaceous material at the REDOX front developed between the two mixing fluids at the point of sandstone coalescence reduced uranyl carbonates in solution. Once reduced the uranium minerals remained stable because the conditions in the REDOX front were only very weakly oxidizing. As floodplain aggradation continued, the upper sandstone was buried and the entire sandstone couplet became reducing, permanently stabilizing the uranium mineralization

Uranium series disequilibrium: application to studies of the groundwater regime of the Harwell region

International Nuclear Information System (INIS)

Ivanovich, M.; Alexander, J.

1985-03-01

Regional groundwater systems incorporating argillaceous formations beneath the Harwell site have been studied as part of a national research programme of investigation into the feasibility of disposal of low and intermediate radioactive wastes into argillaceous rocks. The principal aim of the programme is to establish the groundwater flow patterns using hydrogeological and geochemical methods in association with isotope contents and uranium series disequilibrium and thus provide an independent approach to the study of effective permeabilities of clay lithologies in a sedimentary sequence. Thirty four groundwater samples derived from the high permeability formations in the Harwell region have been analysed for uranium and thorium content and 234 U/ 238 U, 230 Th/ 234 U and 230 Th/ 232 Th activity ratios. The uranium isotopic signatures have been interpreted in terms of the regional groundwater circulation and mixing patterns. The most significant zones of groundwater mixing determined from uranium isotopic data are situated just beneath the edge of the confined strata. These zones coincide with the locations of hydraulic lows in the Great Oolite and the Corallian formations towards which the regional groundwaters move. It is concluded that the uranium isotopic signatures can be used to identify water masses and to evaluate mixing of groundwaters in a sedimentary sequence on a regional scale. (author)

Removal of thorium (IV) ions from aqueous solution by a novel nanoporous ZnO: Isotherms, kinetic and thermodynamic studies.

Science.gov (United States)

Kaynar, Ümit H; Ayvacıklı, Mehmet; Hiçsönmez, Ümran; Kaynar, Sermin Çam

2015-12-01

The adsorption of thorium (IV) from aqueous solutions onto a novel nanoporous ZnO particles prepared by microwave assisted combustion was studied using batch methods under different experimental conditions. The effect of contact time, solution pH, initial concentration and temperature on adsorption process was studied. The ability of this material to remove Th (IV) from aqueous solution was characterises by Langmuir, Freunlinch and Temkin adsorption isotherms. The adsorption percent and distribution coefficient for nanoporous ZnO powders in optimum conditions were 97% ± 1.02; 8080 L kg(-1)for Th (IV), respectively. Based on the Langmuir model, the maximum adsorption capacity of nanoporous ZnO for Th (IV) was found to be 1500 g kg(-1). Thermodynamic parameters were determined and discussed. The results indicated that nanoporous ZnO was suitable as sorbent material for recovery and adsorption of Th (IV) ions from aqueous solutions. The radioactive Th (VI) in surface water, sea water and waste waters from technologies producing nuclear fuels, mining (uranium and thorium) and laboratories working with radioactive materials (uranium and thorium) can be removed with this nanoporous ZnO. Copyright © 2015 Elsevier Ltd. All rights reserved.

Mild hydrothermal crystal growth of new uranium(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30}: Structures, optical and magnetic properties

Energy Technology Data Exchange (ETDEWEB)

Yeon, Jeongho; Smith, Mark D. [Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208 (United States); Tapp, Joshua; Möller, Angela [Department of Chemistry and Texas Center for Superconductivity, University of Houston, Houston, TX 77204 (United States); Loye, Hans-Conrad zur, E-mail: zurloye@mailbox.sc.edu [Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208 (United States)

2016-04-15

Two new uranium(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} (1) and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30} (2), were synthesized through an in situ mild hydrothermal route, and were structurally characterized by single crystal X-ray diffraction. The compounds exhibit complex crystal structures composed of corner- or edge-shared UF{sub 9} and MF{sub 6} (M=Mg, Mn) polyhedra, forming hexagonal channels in the three-dimensional framework, in which ordered or disordered divalent metal and sodium atoms reside. The large hexagonal voids contain the nearly regular M(II)F{sub 6} octahedra and sodium ions, whereas the small hexagonal cavities include M(II) and sodium ions on a mixed-occupied site. Magnetic susceptibility measurements yielded effective magnetic moments of 8.36 and 11.6 µ{sub B} for 1 and 2, respectively, confirming the presence and oxidation states of U(IV) and Mn(II). The large negative Weiss constants indicate the spin gap between a triplet and a singlet state in the U(IV). Magnetization data as a function of applied fields revealed that 2 exhibits paramagnetic behavior due to the nonmagnetic singlet ground state of U(IV) at low temperature. UV–vis diffuse reflectance and X-ray photoelectron spectroscopy data were also analyzed. - Graphical abstract: Two new quaternary U(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30}, were crystallized via an in situ reduction step of U(VI) to U(IV) under mild hydrothermal conditions. The compounds show complex crystal structures based on the 3-D building block of U{sub 6}F{sub 30}. Magnetic property measurements revealed that the U(IV) exhibits a nonmagnetic singlet ground state at low temperature with a spin gap. - Highlights: • Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30} have been synthesized and characterized. • The U(IV) fluorides exhibit complex three-dimensional crystal structures. • The

Study on the agglomeration kinetics of uranium peroxide

International Nuclear Information System (INIS)

Bertrand, M.; Mojica Rodriguez, L.A.; Muhr, H.; Plasari, E.; Auger, F.

2016-01-01

Considering the previous study dealing with thermodynamic and kinetic phenomena (nucleation and crystal growth) during the uranium peroxide precipitation, this work focuses on the agglomeration mechanism. It provides the results obtained from the experiments carried out in a mixed suspension - mixed product removal (MSMPR) mixer operating at steady state. The influence of the operating parameters on the uranium peroxide agglomerates was studied in order to identify the agglomeration kernel. The method is based on the resolution of the population balance equation using the method of moments and the experimental particle size distributions. The results lead to a size-independent kernel directly proportional to the crystal growth rate. Under the stirring conditions studied, the agglomeration appears to be significantly reduced by mixing which results in a kernel inversely proportional to the average shear rate. The agglomeration kinetic law obtained in this study will be used for the process modelling in a further study. (authors)

Study on the agglomeration kinetics of uranium peroxide

Energy Technology Data Exchange (ETDEWEB)

Bertrand, M.; Mojica Rodriguez, L.A. [CEA, Centre de Marcoule, Nuclear Energy Division, RadioChemistry and Process Department, 17171, Bagnols-sur-Ceze 30207 (France); Muhr, H.; Plasari, E. [Reaction and Process Engineering Laboratory, CNRS, University of Lorraine. 1 rue Grandville, BP 20451, Nancy 54001 (France); Auger, F. [Areva Mines/SEPA. 2 route de Lavaugrasse, Bessines-sur-Gartempe 87250 (France)

2016-07-01

Considering the previous study dealing with thermodynamic and kinetic phenomena (nucleation and crystal growth) during the uranium peroxide precipitation, this work focuses on the agglomeration mechanism. It provides the results obtained from the experiments carried out in a mixed suspension - mixed product removal (MSMPR) mixer operating at steady state. The influence of the operating parameters on the uranium peroxide agglomerates was studied in order to identify the agglomeration kernel. The method is based on the resolution of the population balance equation using the method of moments and the experimental particle size distributions. The results lead to a size-independent kernel directly proportional to the crystal growth rate. Under the stirring conditions studied, the agglomeration appears to be significantly reduced by mixing which results in a kernel inversely proportional to the average shear rate. The agglomeration kinetic law obtained in this study will be used for the process modelling in a further study. (authors)

Selective oxidation of propene on bismuth molybdate and mixed oxides of tin and antimony and of uranium and antimony

International Nuclear Information System (INIS)

Pendleton, P.; Taylor, D.

1976-01-01

Propene + 18 0 2 reactions have been studied in a static reaction system on bismuth molybdate and mixed oxides of tin and antimony and of uranium and antimony. The [ 16 0] acrolein content of the total acrolein formed and the proportion of 16 0 in the oxygen of the carbon dioxide by-product have been determined. The results indicate that for each catalyst the lattice is the only direct source of the oxygen in the aldehyde, and that lattice and/or gas phase oxygen is used in carbon dioxide formation. Oxygen anion mobility appears to be greater in the molybdate catalyst than in the other two. (author)

Simulation of uranium and plutonium oxides compounds obtained in plasma

Science.gov (United States)

Novoselov, Ivan Yu.; Karengin, Alexander G.; Babaev, Renat G.

2018-03-01

The aim of this paper is to carry out thermodynamic simulation of mixed plutonium and uranium oxides compounds obtained after plasma treatment of plutonium and uranium nitrates and to determine optimal water-salt-organic mixture composition as well as conditions for their plasma treatment (temperature, air mass fraction). Authors conclude that it needs to complete the treatment of nitric solutions in form of water-salt-organic mixtures to guarantee energy saving obtainment of oxide compounds for mixed-oxide fuel and explain the choice of chemical composition of water-salt-organic mixture. It has been confirmed that temperature of 1200 °C is optimal to practice the process. Authors have demonstrated that condensed products after plasma treatment of water-salt-organic mixture contains targeted products (uranium and plutonium oxides) and gaseous products are environmental friendly. In conclusion basic operational modes for practicing the process are showed.

Long-term performance of elemental iron and hydroxyapatite for uranium retention in permeable reactive barriers used for groundwater remediation

International Nuclear Information System (INIS)

Biermann, V.

2007-01-01

mineral phases could be identified in spent Fe 0 column material. But image analysis (ESEM / EDX) indicates formation of a mixed U(IV)/U(VI) oxide. While HAP long-term performance depends mainly on sorption capacity, maintaining hydraulic conductivity is crucial for Fe 0 . In both cases water compositon has a great influence as well. (orig.)

Experience with thermal recycle of plutonium and uranium

International Nuclear Information System (INIS)

Beer, O.; Schlosser, G.; Spielvogel, F.

1985-01-01

The Federal Republic of Germany (FRG) decided to close the fuel cycle by erecting the reprocessing plant WA350 at Wackersdorf. As long as the plutonium supply from reprocessing plants exceeds the plutonium demand of fast breeder reactors, recycling of plutonium in LWR's is a convenient solution by which a significant advanced uranium utilization is achieved. The demonstration of plutonium recycling performed to date in the FRG in BWR's and PWR's shows that thermal plutonium recycling on an industrial scale is feasible and that the usual levels of reliability and safety can be achieved in reactor operation. The recycling of reprocessed uranium is presently demonstrated in the FRG, too. As regards fuel cycle economy thermal recycling allows savings in natural uranium and separative work. Already under present cost conditions the fuel cycle costs for mixed oxide or enriched reprocessed uranium fuel assemblies are equal or even lower than for usual uranium fuel assemblies

In Situ Community Control of the Stability of Bioreduced Uranium

International Nuclear Information System (INIS)

White, David C.

2006-01-01

The overall objective of this research is to understand the mechanisms for maintenance of bio-reduced uranium in an aerobic to microaerophylic aquifer under actual field conditions after electron donor addition for biostimulation has ended. Primary Objectives: (1) Determine the relative importance of microbial communities and/or chemical and physical environments mediating uranium reduction/oxidation after cessation of donor addition in an aerobic aquifer. (2) Determine, after cessation of donor addition, the linkages between microbial functions and abiotic processes mediating. Initial Hypotheses: (1) The typical bio-reduced subsurface environments that maintain U(VI) reduction rates after biostimulation contain limited amounts of oxidized iron on mineral surfaces. Therefore, the non sulfate-reducing dissimilatory iron reducing bacteria will move to more conducive areas or be out-competed by more versatile microbes. (2) Microbes capable of sulfate reduction play an important role in the post-treatment maintenance of bio-reduced uranium because these bacteria either directly reduce U(VI) or generate H2S, and/or FeS0.9 which act as oxygen sinks maintaining U(IV) in a reduced state. (3) The presence of bioprecipitated amorphous FeS0.9 in sediments will maintain low U(IV) reoxidation rates under conditions of low biomass, but FeS0.9 by itself is not sufficient to remove U(VI) from groundwater by abiotic reduction. FIELD SCALE EXPERIMENTS: Field-scale electron donor amendment experiments were conducted in 2002, 2003, and 2004 at the Old Rifle Uranium Mill Tailings Remedial Action (UMTRA) site in Rifle, Colorado

Determination of kinetic coefficients for the reduction and removal of uranium from water by the Desulfovibrio desulfuricans bacteria

International Nuclear Information System (INIS)

Tucker, M.D.; Barton, L.L.; Thomson, B.M.

1996-01-01

Uranium contamination of groundwater and surface water from abandoned uranium mill tailings piles is a serious concern in many areas of the western United States. U(VI) is soluble in water and, as a result, is relatively mobile in the environment. U(IV), however, is generally insoluble in water and, therefore, is not subject to aqueous transport. In recent years, researchers have discovered that certain microorganisms, such as the sulfate-reducing bacteria Desuffiovibrio desulfricans, can mediate the reduction of U(VI) to U(IV) by anaerobic respiration. Although the ability of this microorganism to reduce U(VI) has been studied in some detail by previous researchers, the kinetics of the reaction have not been characterized. The purpose of this research was to perform kinetic studies on Desuffiovibrio desulfricans during simultaneous reduction of sulfate and uranium and to determine the mineral phase of uranium after it has been reduced. The studies were conducted in a laboratory-scale chemostat under substrate-limited growth conditions with pyruvate as the substrate. The maximum rate of substrate utilization (k) was determined to be 4.70 days -1 while the half-velocity constant (Ks) was 140 mg CODA. The yield coefficient (Y) was determined to be 0. 17 mg cells/mg COD while the endogenous decay coefficient (kd) was found to be 0.072 days -1 . After reduction, U(IV) precipitated from solution in the uraninite (UO 2 ) phase as predicted by thermodynamics. Uranium removal efficiency as high as 90% was achieved in the chemostat

The distribution of depleted uranium contamination in Colonie, NY, USA

International Nuclear Information System (INIS)

Lloyd, N.S.; Chenery, S.R.N.; Parrish, R.R.

2009-01-01

Uranium oxide particles were dispersed into the environment from a factory in Colonie (NY, USA) by prevailing winds during the 1960s and '70s. Uranium concentrations and isotope ratios from bulk soil samples have been accurately measured using inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) without the need for analyte separation chemistry. The natural range of uranium concentrations in the Colonie soils has been estimated as 0.7-2.1 μg g -1 , with a weighted geometric mean of 1.05 μg g -1 ; the contaminated soil samples comprise uranium up to 500 ± 40 μg g -1 . A plot of 236 U/ 238 U against 235 U/ 238 U isotope ratios describes a mixing line between natural uranium and depleted uranium (DU) in bulk soil samples; scatter from this line can be accounted for by heterogeneity in the DU particulate. The end-member of DU compositions aggregated in these bulk samples comprises (2.05 ± 0.06) x 10 -3235 U/ 238 U, (3.2 ± 0.1) x 10 -5236 U/ 238 U, and (7.1 ± 0.3) x 10 -6234 U/ 238 U. The analytical method is sensitive to as little as 50 ng g -1 DU mixed with the natural uranium occurring in these soils. The contamination footprint has been mapped northward from site, and at least one third of the uranium in a soil sample from the surface 5 cm, collected 5.1 km NNW of the site, is DU. The distribution of contamination within the surface soil horizon follows a trend of exponential decrease with depth, which can be approximated by a simple diffusion model. Bioturbation by earthworms can account for dispersal of contaminant from the soil surface, in the form of primary uranium oxide particulates, and uranyl species that are adsorbed to organic matter. Considering this distribution, the total mass of uranium contamination emitted from the factory is estimated to be c. 4.8 tonnes.

The distribution of depleted uranium contamination in Colonie, NY, USA

Energy Technology Data Exchange (ETDEWEB)

Lloyd, N.S., E-mail: nsl3@alumni.leicester.ac.uk [Department of Geology, University of Leicester, University Road, Leicester, LE1 7RH (United Kingdom); Chenery, S.R.N. [British Geological Survey, Kingsley Dunham Centre, Keyworth, Nottingham, NG12 5GG (United Kingdom); Parrish, R.R. [Department of Geology, University of Leicester, University Road, Leicester, LE1 7RH (United Kingdom); NERC Isotope Geosciences Laboratory, Kingsley Dunham Centre, Keyworth, Nottingham, NG12 5GG (United Kingdom)

2009-12-20

Uranium oxide particles were dispersed into the environment from a factory in Colonie (NY, USA) by prevailing winds during the 1960s and '70s. Uranium concentrations and isotope ratios from bulk soil samples have been accurately measured using inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) without the need for analyte separation chemistry. The natural range of uranium concentrations in the Colonie soils has been estimated as 0.7-2.1 {mu}g g{sup -1}, with a weighted geometric mean of 1.05 {mu}g g{sup -1}; the contaminated soil samples comprise uranium up to 500 {+-} 40 {mu}g g{sup -1}. A plot of {sup 236}U/{sup 238}U against {sup 235}U/{sup 238}U isotope ratios describes a mixing line between natural uranium and depleted uranium (DU) in bulk soil samples; scatter from this line can be accounted for by heterogeneity in the DU particulate. The end-member of DU compositions aggregated in these bulk samples comprises (2.05 {+-} 0.06) x 10{sup -3235}U/{sup 238}U, (3.2 {+-} 0.1) x 10{sup -5236}U/{sup 238}U, and (7.1 {+-} 0.3) x 10{sup -6234}U/{sup 238}U. The analytical method is sensitive to as little as 50 ng g{sup -1} DU mixed with the natural uranium occurring in these soils. The contamination footprint has been mapped northward from site, and at least one third of the uranium in a soil sample from the surface 5 cm, collected 5.1 km NNW of the site, is DU. The distribution of contamination within the surface soil horizon follows a trend of exponential decrease with depth, which can be approximated by a simple diffusion model. Bioturbation by earthworms can account for dispersal of contaminant from the soil surface, in the form of primary uranium oxide particulates, and uranyl species that are adsorbed to organic matter. Considering this distribution, the total mass of uranium contamination emitted from the factory is estimated to be c. 4.8 tonnes.

SIMS Analyses of Aerodynamic Fallout from a Uranium-Fueled Test

Energy Technology Data Exchange (ETDEWEB)

Lewis, L. A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Univ. of California, Berkeley, CA (United States); Knight, K. B. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Matzel, J. E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Prussin, S. G. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Ryerson, F. J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Kinman, W. S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Zimmer, M. M. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Hutcheon, I. D. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

2014-09-09

Five silicate fallout glass spherules produced in a uranium-fueled, near-surface nuclear test were characterized by secondary ion mass spectrometry, electron probe microanalysis, autoradiography, scanning electron microscopy, and energy-dispersive x ray spectroscopy. Several samples display distinctive compositional heterogeneity suggestive of incomplete mixing, and exhibit heterogeneity in U isotopes with 0.02 < ²³⁵U/ ²³⁸U < 11.8 among all five samples and 0.02 < ²³⁵U/ ²³⁸U < 7.81 within a single sample. In two samples, the ²³⁵U/ ²³⁸U ratio is correlated with major element composition, consistent with the agglomeration of chemically and isotopically distinct molten precursors. Two samples are quasi-homogeneous with respect to composition and uranium isotopic composition, suggesting extensive mixing possibly due longer residence time in the fireball. Correlated variations between ²³⁴U, ²³⁵U, ²³⁶U and ²³⁸U abundances point to mixing of end-members corresponding to uranium derived from the device and natural U ( ²³⁸U/ ²³⁵U = 0.00725) found in soil.

Uranium contamination of drinking water in Kazakhstan and Uzbekistan

International Nuclear Information System (INIS)

Kawabata, Y.; Aparin, V.; Shiraishi, K.; Ko, S.; Yamamoto, M.; Nagaia, M.; Katayama, Y.

2006-01-01

Uranium is a naturally occurring radioactive metal, and is widely distributed in the Earth's crust. But it is concentrated in certain rock formations. Most of the uranium for nuclear weapon produced in the Soviet Union during the Cold War came from Central Asia. Uranium has negative effects on the human body, both as a carcinogen and as a kidney toxin. WHO (2004) prescribed that uranium concentrations in drinking water should be less than 15 mcg/l for only chemical aspects of uranium addressed. We determined high uranium concentrations in drinking water in the central region of Uzbekistan (Y. KAWABATA et al. 2004). In this area, some discharge water from farmland has higher uranium concentration. Irrigation systems Kyzyl-orda in Republic of Kazakhstan and in Karakalpakstan in the Republic of Uzbekistan have drains deeper than 5 m, in order to protect against salinization. Water in these drains can mix with ground water. In this area, ground water is used for drinking water. We investigated uranium concentrations in water in Kazakhstan and Uzbekistan. In the half of drinking water sampling points, uranium concentrations exceeded the WHO (2004) guideline level for drinking water. Uranium is a suspected carcinogen that can also have a toxic effect on kidney. However, WHO addresses only the chemical aspects of uranium by giving uranium concentrations in drinking water. The effect of uranium exposure from drinking water on people in these areas is significant. The uranium concentration in the Aral Sea was higher than that in sea water. Aral Sea is accumulating uranium. (author)

Heterogeneous catalysis in fluoride melts - reduction of uranium(V) by hydrogen

Energy Technology Data Exchange (ETDEWEB)

Kelmers, A D; Bennett, M R [Oak Ridge National Lab., Tenn. (USA)

1976-01-01

A necessary step in fuel reprocessing for the Molten-Salt Breeder Reactor is the reduction of pentavalent uranium to tetravalent uranium by hydrogen gas. The pentavalent uranium is dissolved in a mixed fluoride melt. Results are presented which show that the hydrogen reduction is rate limited, possibly due to the dissociation of hydrogen molecules to yield active hydrogen atoms; and that by the application of platinum catalysts a 10- to 100-fold increase in the reaction rate can be achieved.

Study of uranium oxidation states in geological material.

Science.gov (United States)

Pidchenko, I; Salminen-Paatero, S; Rothe, J; Suksi, J

2013-10-01

A wet chemical method to determine uranium (U) oxidation states in geological material has been developed and tested. The problem faced in oxidation state determinations with wet chemical methods is that U redox state may change when extracted from the sample material, thereby leading to erroneous results. In order to quantify and monitor U redox behavior during the acidic extraction in the procedure, an analysis of added isotopic redox tracers, (236)U(VI) and (232)U(IV), and of variations in natural uranium isotope ratio ((234)U/(238)U) of indigenous U(IV) and U(VI) fractions was performed. Two sample materials with varying redox activity, U bearing rock and U-rich clayey lignite sediment, were used for the tests. The Fe(II)/Fe(III) redox-pair of the mineral phases was postulated as a potentially disturbing redox agent. The impact of Fe(III) on U was studied by reducing Fe(III) with ascorbic acid, which was added to the extraction solution. We observed that ascorbic acid protected most of the U from oxidation. The measured (234)U/(238)U ratio in U(IV) and U(VI) fractions in the sediment samples provided a unique tool to quantify U oxidation caused by Fe(III). Annealing (sample heating) to temperatures above 500 °C was supposed to heal ionizing radiation induced defects in the material that can disturb U redox state during extraction. Good agreement between two independent methods was obtained for DL-1a material: an average 38% of U(IV) determined by redox tracer corrected wet chemistry and 45% for XANES. Copyright © 2013 Elsevier Ltd. All rights reserved.

Geochemistry of the Cigar Lake uranium deposit: XPS studies

International Nuclear Information System (INIS)

Sunder, S.; Cramer, J.J.; Miller, N.H.

1996-01-01

Samples of uranium ore from the Cigar Lake deposit in northern Saskatchewan, Canada, were analyzed using XPS. High-resolution spectra were recorded for the strongest bands of the major elements (U 4f, C 1 s, O 1 s, Pb 4 f, S 2 p, Cu 2 p, Fe 2 p, and the valence region (0-20 eV)) to obtain chemical state information for these samples. In general, the U VI /U IV ratio was very low, i.e., much less than 0.5, the threshold for the oxidative dissolution of UO 2 . The low values of the U VI /U IV ratio observed for samples from the Cigar Lake deposit indicate thermodynamic stability of the uranium ore in the reduced aqueous environment. Similarities between the disposal vault envisaged in the Canadian Nuclear Fuel Waste Management Program and the Cigar Lake deposit suggest that, if geochemical conditions in the vault were to be similar to those in the deposit, the long-term dissolution of UO 2 fuel would be very minimal. (orig.)

Selective separation of iron from uranium in quantitative determination of traces of uranium by alpha spectrometry in soil/sediment sample.

Science.gov (United States)

Singhal, R K; Narayanan, Usha; Karpe, Rupali; Kumar, Ajay; Ranade, A; Ramachandran, V

2009-04-01

During this work, controlled redox potential methodology was adopted for the complete separation of traces of uranium from the host matrix of mixed hydroxide of Iron. Precipitates of Fe(+2) and Fe(+3) along with other transuranic elements were obtained from acid leached solution of soil by raising the pH to 9 with 14N ammonia solution. The concentration of the uranium observed in the soil samples was 200-600 ppb, whereas in sediment samples, the concentration range was 61-400 ppb.

The collection of uranium from sea water with hydrous metal oxide, 3

International Nuclear Information System (INIS)

Yamashita, Hisao; Nakajima, Fumito; Ozawa, Yoshihiro; Murata, Toshifumi.

1980-01-01

The effect of diverse ions present in sea water on the uranium adsorption is elucidated in the present paper. The uranium-adsorption experiments were conducted using sea water and a solution containing 0.72 mol dm -3 NaCl and 2.3 x 10 -3 mol dm -3 NaHCO 3 . The uranium uptake was about ten times larger from the NaCl-NaHCO 3 solution than from sea water. The ions which depressed the uranium uptake were the calcium, magnesium, and fluoride present in sea water. Among these ions, calcium had the largest effect on the uranium uptake. The analysis of calcium and carbonate in the adsorbent after the adsorption experiment has revealed that the molar ratio between calcium and carbonate was about one. It was considered that calcium carbonate was deposited on the adsorbent during the uranium adsorption. The specific surface area and the pore volume decreased after the deposition of calcium carbonate. It was supposed that the decrease in the uranium uptake was caused by the coverage of the surface of hydrous titanium(IV) oxide with calcium carbonate. Magnesium ions depressed the uranium uptake in the same manner as calcium ions. The effect of the magnesium ions, however, was relatively small compared with that of the calcium ions. (author)

Impact of mixed low-molecular-weight organic acids on uranium accumulation and distribution in a variant of mustard (Brassica juncea var. tumida)

International Nuclear Information System (INIS)

Fangfang Qi; Dingna Wang; Lijian Ma; Yongdong Jin; Liang Du; Dong Zhang; Chuanqin Xia; Sichuan University, Chengdu

2014-01-01

The impact of a mixture of low-molecular-weight organic acids (LMWOAs) composed of CA/MA/OA/LA with a molar ratio of 2.5:2.31:1.15:0.044 on uranium (U) accumulation and distribution in mustard (Brassica juncea var. tumida) was studied in this paper in order to understand the mechanism of rhizosphere-exudation assisted phytoremediation by hydroponic and pot culture experiments. The impact of the mixture of LWMOAs (Mix) on U accumulation showed that in hydroponic conditions Mix could enhance U translocation from root-to-shoot in mustard, but inhibit U uptake in root. In pot experiments, Mix enhanced both root and shoot U accumulation in mustard. The time-dependent kinetics of U uptake in mustard on Mix treatment showed that U content in plant shoots and roots increased with time increasing, and the steady state conditions were obtained at the 8th and 5th day with the U content of 1,528 and 2,300 mg/kg, respectively. Transmission electron microscope and energy dispersive X-ray spectrometry analysis for mustard roots showed that U was mainly observed on cell membrane of mustard roots on Mix treatment. This study would provide new insights for the mixture of LWMOAs-assisted phytoremediation of U-contaminated soil. (author)

Sorption and bioreduction of hexavalent uranium at a military facility by the Chesapeake Bay

International Nuclear Information System (INIS)

Dong Wenming; Xie Guibo; Miller, Todd R.; Franklin, Mark P.; Oxenberg, Tanya Palmateer; Bouwer, Edward J.; Ball, William P.; Halden, Rolf U.

2006-01-01

Directly adjacent to the Chesapeake Bay lies the Aberdeen Proving Ground, a U.S. Army facility where testing of armor-piercing ammunitions has resulted in the deposition of >70,000 kg of depleted uranium (DU) to local soils and sediments. Results of previous environmental monitoring suggested limited mobilization in the impact area and no transport of DU into the nation's largest estuary. To determine if physical and biological reactions constitute mechanisms involved in limiting contaminant transport, the sorption and biotransformation behavior of the radionuclide was studied using geochemical modeling and laboratory microcosms (500 ppb U(VI) initially). An immediate decline in dissolved U(VI) concentrations was observed under both sterile and non-sterile conditions due to rapid association of U(VI) with natural organic matter in the sediment. Reduction of U(VI) to U(IV) occurred only in non-sterile microcosms. In the non-sterile samples, intrinsic bioreduction of uranium involved bacteria of the order Clostridiales and was only moderately enhanced by the addition of acetate (41% vs. 56% in 121 days). Overall, this study demonstrates that the migration of depleted uranium from the APG site into the Chesapeake Bay may be limited by a combination of processes that include rapid sorption of U(VI) species to natural organic matter, followed by slow, intrinsic bioreduction to U(IV). - At the Aberdeen Proving Ground in Maryland, USA, migration of depleted uranium into the Chesapeake Bay is limited by rapid sorption of the radionuclide to natural organic matter followed by slow biological reduction of water-soluble U(VI) to the insoluble and less toxic U(IV) species

Titration of uranium trace amounts in waters environment

International Nuclear Information System (INIS)

Larabi-Gruet, N.; Ithurbide, A.; Poulesquen, A.; Beaucaire, C.; Peulon, S.; Chausse, A.

2007-01-01

In the framework of studies concerning the uranium migration in soils and rocks, it seems necessary to quantify the uranium(VI) dissolved in solution. In the environmental conditions, the uranium(VI) is present at trace amounts. The most adapted method to this study and easy to carry out is the Adsorptive Stripping Voltammetry. By addition of a compound (ligand) with a reducing and strong complexing power, the uranium(VI) present in solution is reduced into a U(VI)-ligand complex. This specie is then oxidized and adsorbed on the mercury droplet where an electrolytic pre-concentration of the element to determine the quantity of is carried out. At last, a cathodic re-dissolution of the specie adsorbed in the U(IV)-ligand complex is carried out. The chosen analytical method is the differential impulsional voltammetry. With this method, it is possible to quantify low electro-active species quantities (sensitivity ∼25 ppt (10 -10 mol.L -1 ) for the uranium). This titration method in solution has been optimized, at first, in a non complexing medium. Then, the uranium in solution has been titrated in media whose composition has been progressively complexed (additions of CO 3 2- , SO 4 2- , Cl - ..) for being at last representative of the environmental interstitial waters. At last, this study has been carried out too by ICP-MS (Inductively Coupled Plasma-Mass Spectrometry) in order to compare the analysis sensitivity of these two detection methods. (O.M.)

Off gas processing device for degreasing furnace for uranium/plutonium mixed oxide fuel

International Nuclear Information System (INIS)

Ueda, Masaya; Akasaka, Takayuki; Noura, Takeshi.

1996-01-01

A low melting ingredient capturing-cooling trap connected to a degreasing sintering furnace by way of sealed pipelines, a burning/decomposing device for decomposing high melting ingredient gases discharged from the cooling trap by burning them and a gas sucking means for forming the flow of off gases are contained in a glovebox, the inside pressure of which is kept negative. Since the degreasing sintering furnace for uranium/plutonium mixed oxide fuels is disposed outside of the glovebox, operation can be performed safely without greatly increasing the scale of the device, and the back flow of gases is prevented easily by keeping the pressure in the inside of the glovebox negative. Further, a heater is disposed at the midway of the sealed pipelines from the degreasing sintering furnace to the cooling trap, the temperature is kept high to prevent deposition of low melting ingredients to prevent clogging of the sealed pipelines. Further, a portion of the pipelines is made extensible in the axial direction to eliminate thermal stresses caused by temperature change thereby enabling to extend the life of the sealed pipelines. (N.H.)

Studying uranium migration in natural environment: experimental approach and geochemical modeling

International Nuclear Information System (INIS)

Phrommavanh, V.

2008-10-01

The present study deals with characterizing uranium migration in a limited zone of Le Bouchet site, a former uranium ore treatment facility, which is dismantled and the rehabilitation of which is under process. Some wastes are packed in a rehabilitated disposal nearby, called the Itteville site. In the framework of the monitoring of the deposit environment (air, water, sediment) set by prefectorial decrees, a piezometer (PZPK) located downstream to the latter, has shown total dissolved uranium peaks each winter since the 1990's. PZPK collects both the interstitial water of a calcareous peat formation, between the surface and 3 m, and an alluvial aquifer near 6 m of depth. Firstly, a hydrogeochemical characterization of the site has evidenced the uranium source term, which is present in the peat soil near 0.8 m, hence excluding any leaching from the waste disposal. Actually, a few microparticles of uranium oxide and mixed uranium-thorium oxide have been detected, but they do not represent the major part of the source term. Secondly, water chemistry of the peat soil water and PZPK has been monitored every two months from 2004 to 2007 in order to understand the reasons of the seasonal fluctuations of [U]tot.diss.. Completed with geochemical modeling and a bacterial identification by 16S rDNA sequence analysis, water chemistry data showed an important sulfate-reducing bacterial activity in summertime, leading to reducing conditions and therefore, a total dissolved uranium content limited by the low solubility of uraninite U IV O 2 (s). In wintertime, the latter bacterial activity being minimal and the effective pluviometry more important, conditions are more oxidant, which favors U(VI), more soluble, notably as the Ca 2 UO 2 (CO 3 ) 3 (aq) complex, evidenced by TRLFS. Finally, bacterial activity has been reproduced in laboratory in order to better characterize its impact on uranium solubility in the peat soil. Various parameters were tested (C sources, temperature

Uranium hetero-bimetallic complexes: synthesis, structure and magnetic properties

International Nuclear Information System (INIS)

Le Borgne, Th.

2000-01-01

The aim of this thesis is to synthesize molecular complexes with uranium and transition metal ions in close proximity, to determine the nature of the magnetic interaction between them. We decided to use Schiff bases as assembling ligands, which are unusual for uranium (IV). Although the simplest Schiff bases, such as H 2 Salen, lead to ligand exchange reactions, the bi-compartmental Schiff base H 4 L 6 (bis(3-hydroxy-salicylidene) - 2,2-dimethyl-propylene) allows the crystal structure determination of the complex [L 6 Cu(pyr)]U[L 6 Cu].2pyr, obtained by reaction of the metallo-ligand H 2 L 6 Cu with U(acac) 4 . In this manner, the complexes [L 6 Co(pyr)] 2 U and [L 6 Ni(pyr)] 2 U.pyr were also isolated, as well as the compounds in which the paramagnetic ions have been exchanged by the diamagnetic ions Zn II , Zr IV and Th IV ': [L 6 Zn(pyr)] 2 U, [L 6 Cu] 2 Zr and [L 6 Cu(pyr)]Th[L 6 Cu].2pyr. These complexes are the first which involve three metallic centres assembling by the means of a hexa-dentate Schiff base. The crystalline structures show, for all these complexes, the outstanding orthogonal arrangement of the two fragments L 6 M around the central atom which is in a dodecahedral environment of eight oxygen atoms of two Schiff bases. The syntheses of the isostructural complexes Cu2 II and Zn 2 U in which the uranium (IV) ion is close, in the first one, to the paramagnetic ion Cu II and, in the second one, to the diamagnetic ion Zn II , has allowed the use of the empiric method to determine the nature of the magnetic interaction between an f element and a transition metal. The comparison of the magnetic behaviour of two complexes Cu 2 U and Zn 2 U, expressed by the variation of χT vs T, reveals the ferromagnetic interaction in the heart of the triad Cu-U-Cu. The magnetic behaviour of the complexes Cu 2 Th et Cu 2 Zr which does not show any coupling between the two copper (II) ions and the weak antiferromagnetic interaction in the Ni 2 U compound, favour the

Uranium hetero-bimetallic complexes: synthesis, structure and magnetic properties; Complexes heterobimetalliques de l'uranium: synthese, structure et proprietes magnetiques

Energy Technology Data Exchange (ETDEWEB)

Le Borgne, Th

2000-10-04

The aim of this thesis is to synthesize molecular complexes with uranium and transition metal ions in close proximity, to determine the nature of the magnetic interaction between them. We decided to use Schiff bases as assembling ligands, which are unusual for uranium (IV). Although the simplest Schiff bases, such as H{sub 2}Salen, lead to ligand exchange reactions, the bi-compartmental Schiff base H{sub 4}L{sup 6} (bis(3-hydroxy-salicylidene) - 2,2-dimethyl-propylene) allows the crystal structure determination of the complex [L{sup 6}Cu(pyr)]U[L{sup 6}Cu].2pyr, obtained by reaction of the metallo-ligand H{sub 2}L{sup 6}Cu with U(acac){sub 4}. In this manner, the complexes [L{sup 6}Co(pyr)]{sub 2}U and [L{sup 6}Ni(pyr)]{sub 2}U.pyr were also isolated, as well as the compounds in which the paramagnetic ions have been exchanged by the diamagnetic ions Zn{sup II}, Zr{sup IV} and Th{sup IV}': [L{sup 6}Zn(pyr)]{sub 2}U, [L{sup 6}Cu]{sub 2}Zr and [L{sup 6}Cu(pyr)]Th[L{sup 6}Cu].2pyr. These complexes are the first which involve three metallic centres assembling by the means of a hexa-dentate Schiff base. The crystalline structures show, for all these complexes, the outstanding orthogonal arrangement of the two fragments L{sup 6}M around the central atom which is in a dodecahedral environment of eight oxygen atoms of two Schiff bases. The syntheses of the isostructural complexes Cu2{sup II} and Zn{sub 2}U in which the uranium (IV) ion is close, in the first one, to the paramagnetic ion Cu{sup II} and, in the second one, to the diamagnetic ion Zn{sup II}, has allowed the use of the empiric method to determine the nature of the magnetic interaction between an f element and a transition metal. The comparison of the magnetic behaviour of two complexes Cu{sub 2}U and Zn{sub 2}U, expressed by the variation of {chi}T vs T, reveals the ferromagnetic interaction in the heart of the triad Cu-U-Cu. The magnetic behaviour of the complexes Cu{sub 2}Th et Cu{sub 2}Zr which does not

Phase equilibrium study on system uranium-plutonium-tungsten-carbon

International Nuclear Information System (INIS)

Ugajin, Mitsuhiro

1976-11-01

Metallurgical properties of the U-Pu-W-C system have been studied with emphasis on phases and reactions. Free energy of compound formation, carbon activity and U/Pu segregation in the W-doped carbide fuel are estimated using phase diagram data. The results indicate that tungsten metal is useful as a thermochemical stabilizer of the carbide fuel. Tungsten has high temperature stability in contact with uranium carbide and mixed uranium-plutonium carbide. (auth.)

Studying uranium migration in natural environment: experimental approach and geochemical modeling; Etude de la migration de l'uranium en milieu naturel: approche experimentale et modelisation geochimique

Energy Technology Data Exchange (ETDEWEB)

Phrommavanh, V.

2008-10-15

The present study deals with characterizing uranium migration in a limited zone of Le Bouchet site, a former uranium ore treatment facility, which is dismantled and the rehabilitation of which is under process. Some wastes are packed in a rehabilitated disposal nearby, called the Itteville site. In the framework of the monitoring of the deposit environment (air, water, sediment) set by prefectorial decrees, a piezometer (PZPK) located downstream to the latter, has shown total dissolved uranium peaks each winter since the 1990's. PZPK collects both the interstitial water of a calcareous peat formation, between the surface and 3 m, and an alluvial aquifer near 6 m of depth. Firstly, a hydrogeochemical characterization of the site has evidenced the uranium source term, which is present in the peat soil near 0.8 m, hence excluding any leaching from the waste disposal. Actually, a few microparticles of uranium oxide and mixed uranium-thorium oxide have been detected, but they do not represent the major part of the source term. Secondly, water chemistry of the peat soil water and PZPK has been monitored every two months from 2004 to 2007 in order to understand the reasons of the seasonal fluctuations of [U]tot.diss.. Completed with geochemical modeling and a bacterial identification by 16S rDNA sequence analysis, water chemistry data showed an important sulfate-reducing bacterial activity in summertime, leading to reducing conditions and therefore, a total dissolved uranium content limited by the low solubility of uraninite U{sup IV}O{sub 2}(s). In wintertime, the latter bacterial activity being minimal and the effective pluviometry more important, conditions are more oxidant, which favors U(VI), more soluble, notably as the Ca{sub 2}UO{sub 2}(CO{sub 3}){sub 3}(aq) complex, evidenced by TRLFS. Finally, bacterial activity has been reproduced in laboratory in order to better characterize its impact on uranium solubility in the peat soil. Various parameters were tested

Pu(IV) reduction with hydroxyurea and its application in U/Pu separation

International Nuclear Information System (INIS)

Zhu Zhaowu; He Jianyu; Zhang Zefu; Song Tianbao; Zhang Yu; Zheng Weifang

2004-01-01

The reduction of Pu(IV) with hydroxyurea (HU) in the mixed phase of 30% TBP/OK-HNO 3 system was studied. The study results show that HU can reduce Pu(IV) to Pu(III) and the reduction rate can be expressed as -dc(Pu(IV))/dt=kc(HU)c -3.2 (HNO 3 )c mix 2 (Pu(IV))c mix -1 (Pu(III)), where k is the rate constant, and k=(896 ± 59) mol 2.3 ·L -2.3 ·min -1 at 15 degree C. With HU serves as a reductant, 16 stages count-current cascade experiment was performed using centrifugal tube to simulate U/Pu separation in the 1B contactor of Purex process. The separation factor of Pu from U and the separation factor of U from Pu reach to 5.4 x 10 4 and 1.8 x 10 5 , respectively. The amount of Pu is about 11 μg in per kg U product. (authors)

Improved locations of reactivity devices in future CANDU reactors fuelled with natural uranium or enriched fuels

International Nuclear Information System (INIS)

Boczar, P.G.; Van Dyk, M.T.

1987-02-01

A new configuration of reactivity devices is proposed for future CANDU reactors which improves the core characteristics with enriched fuels, while still allowing the use of natural uranium fuel. Physics calculations for this new configuration are presented for four fuel types: natural uranium, mixed plutonium - uranium oxide (MOX) having a burnup of 21 MWd/kg, and slightly enriched uranium (SEU) having burnups of either 21 or 31 MWd/kg

Great Basin geologic framework and uranium favorability

International Nuclear Information System (INIS)

Larson, L.T.; Beal, L.H.

1978-01-01

Work on this report has been done by a team of seven investigators assisted over the project span by twenty-three undergraduate and graduate students from May 18, 1976 to August 19, 1977. The report is presented in one volume of text, one volume or Folio of Maps, and two volumes of bibliography. The bibliography contains approximately 5300 references on geologic subjects pertinent to the search for uranium in the Great Basin. Volume I of the bibliography lists articles by author alphabetically and Volume II cross-indexes these articles by location and key word. Chapters I through IV of the Text volume and accompanying Folio Map Sets 1, 2, 3, 4, and 5, discuss the relationship of uranium to rock and structural environments which dominate the Great Basin. Chapter 5 and Map Sets 6 and 7 provide a geochemical association/metallogenic grouping of mineral occurrences in the Great Basin along with information on rock types hosting uranium. Chapter VI summarizes the results of a court house claim record search for 'new' claiming areas for uranium, and Chapter VII along with Folio Map Set 8 gives all published geochronological data available through April 1, 1977 on rocks of the Great Basin. Chapter VIII provides an introduction to a computer analysis of characteristics of certain major uranium deposits in crystalline rocks (worldwide) and is offered as a suggestion of what might be done with uranium in all geologic environments. We believe such analysis will assist materially in constructing exploration models. Chapter IX summarizes criteria used and conclusions reached as to the favorability of uranium environments which we believe to exist in the Great Basin and concludes with recommendations for both exploration and future research. A general summary conclusion is that there are several geologic environments within the Great Basin which have considerable potential and that few, if any, have been sufficiently tested

A density functional theory study of uranium-doped thoria and uranium adatoms on the major surfaces of thorium dioxide

Energy Technology Data Exchange (ETDEWEB)

Shields, Ashley E. [Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom); Santos-Carballal, David [School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT (United Kingdom); Leeuw, Nora H. de, E-mail: DeLeeuwN@Cardiff.ac.uk [Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom); School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT (United Kingdom)

2016-05-15

Thorium dioxide is of significant research interest for its use as a nuclear fuel, particularly as part of mixed oxide fuels. We present the results of a density functional theory (DFT) study of uranium-substituted thorium dioxide, where we found that increasing levels of uranium substitution increases the covalent nature of the bonding in the bulk ThO{sub 2} crystal. Three low Miller index surfaces have been simulated and we propose the Wulff morphology for a ThO{sub 2} particle and STM images for the (100), (110), and (111) surfaces studied in this work. We have also calculated the adsorption of a uranium atom and the U adatom is found to absorb strongly on all three surfaces, with particular preference for the less stable (100) and (110) surfaces, thus providing a route to the incorporation of uranium into a growing thoria particle. - Highlights: • Uranium substitution in ThO{sub 2} is found to increase the covalent nature of the ionic bonding. • The (111), (110), and (100) surfaces of ThO{sub 2} are studied and the particle morphology is proposed. • STM images of the (111), (110), and (100) surfaces of ThO{sub 2} are simulated. • Uranium adsorption on the major surfaces of ThO{sub 2} is studied.

Pretreatment with U(IV) solution for improving the decontamination of ruthenium

International Nuclear Information System (INIS)

Huang Haoxin; Qi Zhanshun; Zhu Guohui

1993-01-01

The ruthenium decontamination factor in Purex process falls quickly in successive TBP cycles. So, it is necessary to change the chemical states of RuNO complexes in order to improve DF Ru in the uranium purification cycle. Hydrazine nitrate is being used to transform RuNO complexes into in-extractable Ru(III)and Ru(IV). However, hydrazine nitrate may be inverted into hydrazoic acid which is dangerous and can bring an unstable factor. Pretreatment using U(IV) solution provides another method to improve the decontamination of ruthenium in Purex process. 0.02 mol/lU(IV) solution can transform RuNO complexes into inextricable species by heating in water bath. The D Ru can be decreased by a factor of 10-20. U(IV) pretreatment does not bring any harmful chemical in process. The acidity has a very large influence on the effect of pretreatment. The higher the acidity is, the worse the effect will be

Clinical validation of three short forms of the Dutch Wechsler Memory Scale-Fourth Edition (WMS-IV-NL) in a mixed clinical sample.

Science.gov (United States)

Bouman, Zita; Hendriks, Marc P H; Van Der Veld, William M; Aldenkamp, Albert P; Kessels, Roy P C

2016-06-01

The reliability and validity of three short forms of the Dutch version of the Wechsler Memory Scale-Fourth Edition (WMS-IV-NL) were evaluated in a mixed clinical sample of 235 patients. The short forms were based on the WMS-IV Flexible Approach, that is, a 3-subtest combination (Older Adult Battery for Adults) and two 2-subtest combinations (Logical Memory and Visual Reproduction and Logical Memory and Designs), which can be used to estimate the Immediate, Delayed, Auditory and Visual Memory Indices. All short forms showed good reliability coefficients. As expected, for adults (16-69 years old) the 3-subtest short form was consistently more accurate (predictive accuracy ranged from 73% to 100%) than both 2-subtest short forms (range = 61%-80%). Furthermore, for older adults (65-90 years old), the predictive accuracy of the 2-subtest short form ranged from 75% to 100%. These results suggest that caution is warranted when using the WMS-IV-NL Flexible Approach short forms to estimate all four indices. © The Author(s) 2015.

Present status of uranium-plutonium mixed carbide fuel development for LMFBRs

International Nuclear Information System (INIS)

Handa, Muneo; Suzuki, Yasufumi

1984-01-01

The feature of carbide fuel is that it has the doubling time as short as about 13 years, that is, close to one half as compared with oxide fuel. The development of the carbide fuel in the past 10 years has been started in amazement. Especially in the program of new fuel development in USA started in 1974, He and Na bond fuel attained the burnup of 16 a/o without causing the breaking of cladding tubes. In 1984, the irradiation of the assembly composed of 91 fuel pins in the FFTF is expected. On the other hand in Japan, the fuel research laboratory was constructed in 1974 in the Oarai Laboratory, Japan Atomic Energy Research Institute, to carry out the studies on carbide fuel. In the autumn of 1982, two carbide fuel pins with different chemical composition have been successfully made. Accordingly, the recent status of the development is explained. The uranium-plutonium mixed carbide fuel is suitable to liquid metal-cooled fast breeder reactors because of large heat conductivity and the high density of nuclear fission substances. The thermal and nuclear characteristics of carbide fuel, the features of the reactor core using carbide fuel, the chemical and mechanical interaction of fuel and cladding tubes, the selection of bond materials, the manufacturing techniques for the fuel, the development of the analysis code for fuel behavior, and the research and development of carbide fuel in Japan are described. (Kako, I.)

RL-1: a certified uranium reference ore

International Nuclear Information System (INIS)

Steger, H.F.; Bowman, W.S.

1985-06-01

A 145-kg sample of a uranium ore from Rabbit Lake, Saskatchewan, has been prepared as a compositional reference material. RL-1 was ground to minus 74 μm and mixed in one lot. Approximately one half of this ore was bottled in 100-g units, the remainder being stored in bulk. The homogeneity of RL-1 with respect to uranium and nickel was confirmed by neutron activation and X-ray fluorescence analytical techniques. In a 'free choice' analytical program, 13 laboratories contributed results for one or more of uranium, nickel and arsenic in one bottle of RL-1. Based on a statistical analysis of the data, the following recommended values were assigned: U, 0.201%; Ni, 185 μg/g; and As, 19.6 μg/g

Liquid liquid extraction of Th(IV) and its complexation study by Calix(4)pyrole

International Nuclear Information System (INIS)

Rathod, N.V.; Kamble, J.H.; Malkhede, D.D.

2015-01-01

Due to increased demand for carbon-free energy, accelerated growth of nuclear power is foreseen in several countries, especially in China and India. This has made the sustainable use of fuel resources such as uranium and thorium very important. Today, uranium is the main-stay of the present generation of nuclear power plants. However, the anticipated growth in nuclear energy may require introducing thorium as a fuel in future. Meso-octamethyl calix(4)pyrole is known for anion receptor however the present study evaluate the effect of cation for complexation of thorium by liquid liquid extraction technique. Calix(4)pyrole was evaluated for extraction of Th(IV), and 97% extraction efficiency was obtained. Th(IV) was determine with arsenazo(III) at 655 nm. The effect of acid molarity of 0.1 M, 1:5 metal to ligand ratio found efficient for maximum extraction. The stoichiometry ratio 1:2 between metal to ligand is established

Concentration of uranium-235 in mixtures with uranium-238 using ion exchange resins

International Nuclear Information System (INIS)

Seko, M.; Kakihana, H.

1976-01-01

A method is described of simultaneously obtaining separate enriched fractions of 235 U and 238 U from isotopic mixtures thereof with the use of an ion exchange column by passing a liquid body containing the isotopic mixture through the column. The uranium as it is passed through the column is presented as a U(IV) coordination compound with a ligand at different valent states and is followed by an eluant and forms a band which travels through the column, the front and rear portions of which are respectively enriched in one of the isotopes and depleted in the other. 16 claims

Recovery treatment for the non fissioned uranium in the production of Mo-99

International Nuclear Information System (INIS)

Rodriguez S, A.; Acosta C, A.L.; Lopez M, B.E.

1991-09-01

An effective modification of the chemical processes has been obtained to dissolve at the uranium-IV and to extract it as uranyl triperoxidate that facilitates its manipulation and final conversion to uranyl nitrate like a concentrate of high purity. (Author)

Potentiometric determination of uranium in simulated Purex Process solutions by acidiometry

International Nuclear Information System (INIS)

Cohen, V.H.; Matsuda, H.T.; Araujo, B.F. de; Araujo, J.A. de

1983-01-01

A potentiometric methods for sequential free acidity and uranium determination in simulated Purex Process solutions is described. An oxalate solution or a mixture of fluoride-oxalate pellets were used as complexing agent for free titration. Following this first equivalent point, uranium is determined-by indirect titration of H + liberated in the peruanate reaction. Some elements present in the standard fuel elements with a burn-up of 33.000 Mwd/t, neutron flux of 3,2 x 10 13 n.cm -2 .s -1 and cooling time of two years were considered as interfering elements in uranium analyses. As a substitute of Pu-IV, Th(NO 3 ) 4 solution was used. The method can be applied to aqueous and organic (TBP/diluent) solutions with 2% precision and 2% accuracy. (Autor) [pt

Potentiometric determination of uranium in simulated Purex Process solutions by acidiometry

Energy Technology Data Exchange (ETDEWEB)

Cohen, V H; Matsuda, H T; Araujo, B.F. de; Araujo, J.A. de

1984-01-01

A potentiometric methods for sequential free acidity and uranium determination in simulated Purex Process solutions is described. An oxalate solution or a mixture of fluoride-oxalate pellets were used as complexing agent for free titration. Following this first equivalent point, uranium is determined-by indirect titration of H/sup +/ liberated in the peruanate reaction. Some elements present in the standard fuel elements with a burn-up of 33.000 Mwd/t, neutron flux of 3,2 x 10/sup 13/n.cm/sup -2/.s/sup -1/ and cooling time of two years were considered as interfering elements in uranium analyses. As a substitute of Pu-IV, Th(NO/sub 3/)/sub 4/ solution was used. The method can be applied to aqueous and organic (TBP/diluent) solutions with 2% precision and 2% accuracy. (Autor).

Uranium tailings reference materials

International Nuclear Information System (INIS)

Smith, C.W.; Steger, H.F.; Bowman, W.S.

1984-01-01

Samples of uranium tailings from Bancroft and Elliot Lake, Ontario, and from Beaverlodge and Rabbit Lake, Saskatchewan, have been prepared as compositional reference materials at the request of the National Uranium Tailings Research Program. The four samples, UTS-1 to UTS-4, were ground to minus 104 μm, each mixed in one lot and bottled in 200-g units for UTS-1 to UTS-3 and in 100-g units for UTS-4. The materials were tested for homogeneity with respect to uranium by neutron activation analysis and to iron by an acid-decomposition atomic absorption procedure. In a free choice analytical program, 18 laboratories contributed results for one or more of total iron, titanium, aluminum, calcium, barium, uranium, thorium, total sulphur, and sulphate for all four samples, and for nickel and arsenic in UTS-4 only. Based on a statistical analysis of the data, recommended values were assigned to all elements/constituents, except for sulphate in UTS-3 and nickel in UTS-4. The radioactivity of thorium-230, radium-226, lead-210, and polonium-210 in UTS-1 to UTS-4 and of thorium-232, radium-228, and thorium-228 in UTS-1 and UTS-2 was determined in a radioanalytical program composed of eight laboratories. Recommended values for the radioactivities and associated parameters were calculated by a statistical treatment of the results

Selective separation of uranium using alizarin red S (ARS)-modified anion-exchange resin or by flotation of U-ARS chelate

International Nuclear Information System (INIS)

Khalifa, M.E.

1998-01-01

An alizarin red S (ARS)-modified anion exchange resin was prepared by a simple reaction of ARS with the anion exchange Doulite A101 and used for the efficient sorption of uranium from aqueous media. The effect of various parameters on the sorption of U(VI) (pH effect, sorption kinetics, resin capacity and breakthrough curves) was investigated. The modified resin sorbs U(VI) over a wide range of pH (2.8--5) with a maximum sorption capacity of 0.68 mmol/g at pH 3.2 to 4.0. Iron(III), Zr(IV), Ti(IV), Cu(II), and Th(IV) ions are also sorbed to different extents, but Be(II), Bi(III), Ca(II), Mg(II), Pb(II), Hg(II), Zn(II), Cd(II), Al(III), Mn(II), Co(II) and Ni(II) are not sorbed; thus, conditions for separating U(VI) from these metal ions have been identified. For eluting U(VI) from the resin, 0.2 mol/L HCl was used and the recovery recorded was as high as 99.9%. The use of ARS is extended to float uranium quantitatively and selectively from aqueous media at pH ∼ 4 by using oleic acid as a surfactant. The different parameters affecting the flotation process have also been investigated. Uranium(VI) has been effectively separated from natural water samples and certified uranium ores using both procedures

Extraction equilibrium of uranium(VI) with dicyclohexano-18-crown-6 and its application for separating uranium and thorium

International Nuclear Information System (INIS)

Wang Wenji; Sun Quing; Chen Bozhong

1986-01-01

The extraction of uranium with dicyclohexano-18-crown-6 (mixed isomers) is described. The extraction equilibrium of uranium(VI) from aqueous hydrochloric acid solution with dicyclohexano-18-crown-6 isomer A (Isub(a)) and isomer B (Isub(b)) in 1,2-dichloroethane is presented. The extracted species were found to be 1:2 (metal/crown) for Isub(a) and 2:3 for Isub(b) from slope analysis and direct determination of extracted complexes. The extraction equilibrium constants (Ksub(ex)) were determined at 25 deg C and are equal to 29.5 and 0.208, respectively. It is concluded that Isub(a) has a stronger coordination ability for uranium than Isub(b). The different orientation of lone pairs of the oxygen atoms in both isomers has to be taken into account for interpereting the above results. (author)

Uranium

International Nuclear Information System (INIS)

Hamdoun, N.A.

2007-01-01

The article includes a historical preface about uranium, discovery of portability of sequential fission of uranium, uranium existence, basic raw materials, secondary raw materials, uranium's physical and chemical properties, uranium extraction, nuclear fuel cycle, logistics and estimation of the amount of uranium reserves, producing countries of concentrated uranium oxides and percentage of the world's total production, civilian and military uses of uranium. The use of depleted uranium in the Gulf War, the Balkans and Iraq has caused political and environmental effects which are complex, raising problems and questions about the effects that nuclear compounds left on human health and environment.

Uranium extraction from gold-uranium ores

Energy Technology Data Exchange (ETDEWEB)

Laskorin, B.N.; Golynko, Z.Sh.

1981-01-01

The process of uranium extraction from gold-uranium ores in the South Africa is considered. Flowsheets of reprocessing gold-uranium conglomerates, pile processing and uranium extraction from the ores are presented. Continuous counter flow ion-exchange process of uranium extraction using strong-active or weak-active resins is noted to be the most perspective and economical one. The ion-exchange uranium separation with the succeeding extraction is also the perspective one.

Field Testing of Downgradient Uranium Mobility at an In-Situ Recovery Uranium Mine

Science.gov (United States)

Reimus, P. W.; Clay, J. T.; Rearick, M.; Perkins, G.; Brown, S. T.; Basu, A.; Chamberlain, K.

2015-12-01

In-situ recovery (ISR) mining of uranium involves the injection of O2 and CO2 (or NaHCO3) into saturated roll-front deposits to oxidize and solubilize the uranium, which is then removed by ion exchange at the surface and processed into U3O8. While ISR is economical and environmentally-friendly relative to conventional mining, one of the challenges of extracting uranium by this process is that it leaves behind a geochemically-altered aquifer that is exceedingly difficult to restore to pre-mining geochemical conditions, a regulatory objective. In this research, we evaluated the ability of the aquifer downgradient of an ISR mining area to attenuate the transport of uranium and other problem constituents that are mobilized by the mining process. Such an evaluation can help inform both regulators and the mining industry as to how much restoration of the mined ore zone is necessary to achieve regulatory compliance at various distances downgradient of the mining zone even if complete restoration of the ore zone proves to be difficult or impossible. Three single-well push-pull tests and one cross-well test were conducted in which water from an unrestored, previously-mined ore zone was injected into an unmined ore zone that served as a geochemical proxy for the downgradient aquifer. In all tests, non-reactive tracers were injected with the previously-mined ore zone water to allow the transport of uranium and other constituents to be compared to that of the nonreactive species. In the single-well tests, it was shown that the recovery of uranium relative to the nonreactive tracers ranged from 12-25%, suggesting significant attenuation capacity of the aquifer. In the cross-well test, selenate, molybdate and metavanadate were injected with the unrestored water to provide information on the transport of these potentially-problematic anionic constituents. In addition to the species-specific transport information, this test provided valuable constraints on redox conditions within